ORGANIC ELECTROLUMINESCENT MATERIAL AND DEVICE THEREOF
20220393115 · 2022-12-08
Assignee
Inventors
- Hongbo Li (Beijing, CN)
- Ming Sang (Beijing, CN)
- Wei Cai (Beijing, CN)
- Zhen Wang (Beijing, CN)
- Chi Yuen Raymond Kwong (Beijing, CN)
- Chuanjun Xia (Beijing, CN)
Cpc classification
C09K2211/185
CHEMISTRY; METALLURGY
H10K2101/30
ELECTRICITY
C09K2211/1029
CHEMISTRY; METALLURGY
C07B2200/05
CHEMISTRY; METALLURGY
Y02E10/549
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
International classification
Abstract
Provided are an organic electroluminescent material and a device thereof. The organic electroluminescent material is a metal complex comprising a ligand L.sub.a having a structure of Formula 1. The metal complex may be used as a light-emitting material in an electroluminescent device. These novel compounds may be applied to electroluminescent devices and can exhibit better performance, achieve higher device efficiency, and significantly improve the overall performance of the devices. Further provided are an electroluminescent device comprising the metal complex and a compound combination comprising the metal complex.
Claims
1. A metal complex, comprising a metal M and a ligand L.sub.a coordinated to the metal M, wherein the metal M is selected from a metal with a relative atomic mass greater than 40, and the ligand L.sub.a has a structure represented by Formula 1: ##STR00061## wherein in Formula 1, Cy is, at each occurrence identically or differently, selected from a substituted or unsubstituted aromatic ring having 6 to 24 ring atoms, a substituted or unsubstituted heteroaromatic ring having 5 to 24 ring atoms or a combination thereof; X is selected from the group consisting of O, S, Se, NR′, CR′R′, SiR′R′ and GeR′R′, wherein when two R′ are present at the same time, the two R′ are the same or different; X.sub.1 to X.sub.7 are, at each occurrence identically or differently, selected from C, CR.sub.x or N, and at least one of X.sub.1 to X.sub.4 is C and joined to the Cy; X.sub.1, X.sub.2, X.sub.3 or X.sub.4 is joined to the metal M by a metal-carbon bond or a metal-nitrogen bond; A has a structure represented by Formula 2: ##STR00062## E and F are, at each occurrence identically or differently, selected from C, CR″, N, SiR″ or GeR″; R.sub.a1 and R.sub.a2 represent, at each occurrence identically or differently, mono-substitution, multiple substitutions or non-substitution; the ring A.sub.1 and the ring A.sub.2 are fused through E and F, and the ring A.sub.1 and the ring A.sub.2 satisfy one of the following two cases: a first case: the ring A.sub.1 is selected from an alicyclic ring having 3 to 30 ring atoms, a heterocyclic ring having 3 to 30 ring atoms or a combination thereof; and the ring A.sub.2 is selected from an alicyclic ring having 3 to 30 ring atoms, an aromatic ring having 6 to 30 ring atoms, a heterocyclic ring having 3 to 30 ring atoms, a heteroaromatic ring having 5 to 30 ring atoms or a combination thereof; a second case: the ring A.sub.1 is selected from an aromatic ring having 6 to 30 ring atoms, a heteroaromatic ring having 5 to 30 ring atoms or a combination thereof; and the ring A.sub.2 is selected from an alicyclic ring having 3 to 30 ring atoms, a heterocyclic ring having 3 to 30 ring atoms or a combination thereof; R′, R″, R.sub.x, R.sub.a1 and R.sub.a2 are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof; adjacent substituents R′, R″, R.sub.x, R.sub.a1, R.sub.a2 can be optionally joined to form a ring; and “*” represents a position where A is joined.
2. The metal complex of claim 1, wherein Cy is selected from any structure in the group consisting of the following: ##STR00063## wherein R represents, at each occurrence identically or differently, mono-substitution, multiple substitutions or non-substitution; and when multiple R are present at the same time in any structure, the multiple R are the same or different; R is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof; adjacent substituents R can be optionally joined to form a ring; wherein “#” represents a position where Cy is joined to the metal M, and ##STR00064## represents a position where Cy is joined to X.sub.1, X.sub.2, X.sub.3 or X.sub.4.
3. The metal complex of claim 1, wherein the metal complex has a general formula of M(L.sub.a).sub.m(L.sub.b).sub.n(L.sub.c).sub.q; wherein M is, at each occurrence identically or differently, selected from the group consisting of Cu, Ag, Au, Ru, Rh, Pd, Os, Ir and Pt; preferably, M is, at each occurrence identically or differently, selected from Pt or Ir; L.sub.a, L.sub.b and L.sub.c are a first ligand, a second ligand and a third ligand coordinated to the metal M, respectively, and L.sub.c is the same as or different from L.sub.a or L.sub.b; wherein L.sub.a, L.sub.b and L.sub.c can be optionally joined to form a multidentate ligand; m is selected from 1, 2 or 3, n is selected from 0, 1 or 2, q is selected from 0, 1 or 2, and m+n+q equals an oxidation state of the metal M; wherein when m is greater than or equal to 2, a plurality of L.sub.a are the same or different; when n is equal to 2, two L.sub.b are the same or different; when q is equal to 2, two L.sub.c are the same or different; L.sub.a is, at each occurrence identically or differently, selected from the group consisting of the following: ##STR00065## ##STR00066## ##STR00067## ##STR00068## ##STR00069## ##STR00070## ##STR00071## X is selected from the group consisting of O, S, Se, NR′, CR′R′, SiR′R′ and GeR′R′, wherein when two R′ are present at the same time, the two R′ are the same or different; R and R.sub.x represent, at each occurrence identically or differently, mono-substitution, multiple substitutions or non-substitution; A has a structure represented by Formula 2: ##STR00072## E and F are, at each occurrence identically or differently, selected from C, CR″, N, SiR″ or GeR″; R.sub.a1 and R.sub.a2 represent, at each occurrence identically or differently, mono-substitution, multiple substitutions or non-substitution; the ring A.sub.1 and the ring A.sub.2 are fused through E and F, and the ring A.sub.1 and the ring A.sub.2 satisfy one of the following two cases: the first case: the ring A.sub.1 is selected from an alicyclic ring having 3 to 30 ring atoms, a heterocyclic ring having 3 to 30 ring atoms or a combination thereof; and the ring A.sub.2 is selected from an alicyclic ring having 3 to 30 ring atoms, an aromatic ring having 6 to 30 ring atoms, a heterocyclic ring having 3 to 30 ring atoms, a heteroaromatic ring having 5 to 30 ring atoms or a combination thereof; the second case: the ring A.sub.1 is selected from an aromatic ring having 6 to 30 ring atoms, a heteroaromatic ring having 5 to 30 ring atoms or a combination thereof; and the ring A.sub.2 is selected from an alicyclic ring having 3 to 30 ring atoms, a heterocyclic ring having 3 to 30 ring atoms or a combination thereof; “*” represents a position where A is joined; adjacent substituents R, R′, R″, R.sub.x, R.sub.a1, R.sub.a2 can be optionally joined to form a ring; L.sub.b and L.sub.c are, at each occurrence identically or differently, selected from a structure represented by any one of the group consisting of the following: ##STR00073## wherein X.sub.b is, at each occurrence identically or differently, selected from the group consisting of O, S, Se, NR.sub.N1 and CR.sub.C1R.sub.C2; R.sub.a and R.sub.b represent, at each occurrence identically or differently, mono-substitution, multiple substitutions or non-substitution; R, R′, R″, R.sub.x, R.sub.a1, R.sub.a2, R.sub.a, R.sub.b, R.sub.c, R.sub.N1, R.sub.C1 and R.sub.C2 are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof; and adjacent substituents R.sub.a, R.sub.b, R.sub.c, R.sub.N1, R.sub.C1 and R.sub.C2 can be optionally joined to form a ring.
4. The metal complex of claim 1, wherein the metal complex Ir(L.sub.a).sub.m(L.sub.b).sub.3-m has a structure represented by Formula 3: ##STR00074## wherein m is selected from 1, 2 or 3; when m is selected from 1, two L.sub.b are the same or different; when m is selected from 2 or 3, a plurality of L.sub.a are the same or different; Y.sub.1 to Y.sub.4 are, at each occurrence identically or differently, selected from CR.sub.y or N; X is selected from the group consisting of O, S, Se, NR′, SiR′R′ and GeR′R′, wherein when two R′ are present at the same time, the two R′ are the same or different; X.sub.3 to X.sub.7 are, at each occurrence identically or differently, selected from CR.sub.x or N; A has a structure represented by Formula 2: ##STR00075## E and F are, at each occurrence identically or differently, selected from C, CR″, N, SiR″ or GeR″; R.sub.a1 and R.sub.a2 represent, at each occurrence identically or differently, mono-substitution, multiple substitutions or non-substitution; the ring A.sub.1 and the ring A.sub.2 are fused through E and F, and the ring A.sub.1 and the ring A.sub.2 satisfy one of the following two cases: the first case: the ring A.sub.1 is selected from an alicyclic ring having 3 to 30 ring atoms, a heterocyclic ring having 3 to 30 ring atoms or a combination thereof; and the ring A.sub.2 is selected from an alicyclic ring having 3 to 30 ring atoms, an aromatic ring having 6 to 30 ring atoms, a heterocyclic ring having 3 to 30 ring atoms, a heteroaromatic ring having 5 to 30 ring atoms or a combination thereof; the second case: the ring A.sub.1 is selected from an aromatic ring having 6 to 30 ring atoms, a heteroaromatic ring having 5 to 30 ring atoms or a combination thereof; and the ring A.sub.2 is selected from an alicyclic ring having 3 to 30 ring atoms, a heterocyclic ring having 3 to 30 ring atoms or a combination thereof; R′, R″, R.sub.x, R.sub.y, R.sub.a1, R.sub.a2 and R.sub.1 to R.sub.8 are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof; adjacent substituents R′, R″, R.sub.x, R.sub.y, R.sub.a1, R.sub.a2 can be optionally joined to form a ring; adjacent substituents R.sub.1 to R.sub.8 can be optionally joined to form a ring; and “*” represents a position where A is joined.
5. The metal complex of claim 4, wherein X.sub.3 to X.sub.7 are, at each occurrence identically or differently, selected from CR.sub.x, and/or Y.sub.1 to Y.sub.4 are, at each occurrence identically or differently, selected from CR.sub.y.
6. The metal complex of claim 4, wherein at least one of X.sub.3 to X.sub.7 is N, and/or at least one of Y.sub.1 to Y.sub.4 is N.
7. The metal complex of claim 1, wherein X is selected from O or S.
8. The metal complex of claim 1, wherein R.sub.x is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 20 carbon atoms, cyano and combinations thereof; preferably, R.sub.x is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, fluorine, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms, substituted or unsubstituted aryl having 6 to 12 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 12 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 6 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 6 carbon atoms, cyano and combinations thereof; more preferably, R.sub.x is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, fluorine, cyano, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, cyclopentyl, cyclohexyl, deuterated methyl, deuterated ethyl, deuterated propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated t-butyl, deuterated cyclopentyl, deuterated cyclohexyl, phenyl, pyridyl, trimethylsilyl, trimethylgermanyl and combinations thereof.
9. The metal complex of claim 4, wherein at least one of X.sub.3 to X.sub.7 is selected from CR.sub.x, and R.sub.x is cyano or fluorine; preferably, at least one of X.sub.5 to X.sub.7 is selected from CR.sub.x, and R.sub.x is cyano or fluorine; more preferably, X.sub.7 is selected from CR.sub.x, and R.sub.x is cyano or fluorine.
10. The metal complex of claim 1, wherein the ring A.sub.1 is selected from an alicyclic ring having 3 to 10 ring atoms, a heterocyclic ring having 3 to 10 ring atoms or a combination thereof; and the ring A.sub.2 is selected from an alicyclic ring having 3 to 10 ring atoms, an aromatic ring having 6 to 18 ring atoms, a heterocyclic ring having 3 to 10 ring atoms, a heteroaromatic ring having 5 to 18 ring atoms or a combination thereof; preferably, the ring A.sub.1 is selected from cyclopentane, cyclopentene, cyclohexane, cyclohexene, cycloheptane, cycloheptene or the following groups containing one heteroatom or at least two heteroatoms of nitrogen, oxygen, sulfur, selenium, silicon and germanium: heterocyclopentane, heterocyclopentene, heterocyclohexane, heterocyclohexene, heterocycloheptane and heterocycloheptene; and the ring A.sub.2 is selected from benzene, naphthalene, phenanthrene, triphenylene, pyridine, pyrimidine, pyrazine, pyridazine, triazine, pyrrole, furan, thiophene, imidazole, thiazole, oxazole, cyclopentane, cyclopentene, cyclohexane, cyclohexene, cycloheptane, cycloheptene or the following groups containing one heteroatom or at least two heteroatoms of nitrogen, oxygen, sulfur, selenium, silicon and germanium: heterocyclopentane, heterocyclopentene, heterocyclohexane, heterocyclohexene, heterocycloheptane and heterocycloheptene.
11. The metal complex of claim 1, wherein the ring A.sub.1 is selected from an aromatic ring having 6 to 18 ring atoms, a heteroaromatic ring having 5 to 18 ring atoms or a combination thereof; and the ring A.sub.2 is selected from an alicyclic ring having 3 to 10 ring atoms, a heterocyclic ring having 3 to 10 ring atoms or a combination thereof; preferably, the ring A.sub.1 is selected from benzene, naphthalene, phenanthrene, triphenylene, pyridine, pyrimidine, pyrazine, pyridazine, triazine, pyrrole, furan, thiophene, imidazole, thiazole or oxazole; and the ring A.sub.2 is selected from cyclopentane, cyclopentene, cyclohexane, cyclohexene, cycloheptane, cycloheptene or the following groups containing one heteroatom or at least two heteroatoms of nitrogen, oxygen, sulfur, selenium, silicon and germanium: heterocyclopentane, heterocyclopentene, heterocyclohexane, heterocyclohexene, heterocycloheptane and heterocycloheptene.
12. The metal complex of claim 1, wherein R.sub.a1 and R.sub.a2 are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, a hydroxyl group, a sulfanyl group, a cyano group and combinations thereof; preferably, R.sub.a1 and R.sub.a2 are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms, cyano and combinations thereof; more preferably, R.sub.a1 and R.sub.a2 are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, cyano, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, cyclopentyl, cyclohexyl, deuterated methyl, deuterated ethyl, deuterated propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated t-butyl, deuterated cyclopentyl, deuterated cyclohexyl, trimethylsilyl and combinations thereof.
13. The metal complex of claim 1, wherein A is, at each occurrence identically or differently, selected from the group consisting of A-1 to A-264: ##STR00076## ##STR00077## ##STR00078## ##STR00079## ##STR00080## ##STR00081## ##STR00082## ##STR00083## ##STR00084## ##STR00085## ##STR00086## ##STR00087## ##STR00088## ##STR00089## ##STR00090## ##STR00091## ##STR00092## ##STR00093## ##STR00094## ##STR00095## ##STR00096## ##STR00097## ##STR00098## ##STR00099## ##STR00100## ##STR00101## ##STR00102## ##STR00103## ##STR00104## ##STR00105## ##STR00106## ##STR00107## ##STR00108## ##STR00109## ##STR00110## ##STR00111## ##STR00112## ##STR00113## ##STR00114## ##STR00115## ##STR00116## ##STR00117## ##STR00118## ##STR00119## ##STR00120## ##STR00121## wherein optionally, hydrogens in the above groups can be partially or fully deuterated; and “*” represents a position where A is joined.
14. The metal complex of claim 4, wherein R.sub.y is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms and combinations thereof; preferably, at least one R.sub.y is selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms and combinations thereof.
15. The metal complex of claim 4, wherein at least one or at least two of R.sub.5 to R.sub.8 are selected from substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms or a combination thereof; and the total number of carbon atoms in all of R.sub.5 to R.sub.8 is at least 4.
16. The metal complex of claim 4, wherein at least one, at least two, at least three or all of R.sub.2, R.sub.3, R.sub.6 and R.sub.7 are selected from the group consisting of: deuterium, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms and combinations thereof; preferably, at least one, at least two, at least three or all of R.sub.2, R.sub.3, R.sub.6 and R.sub.7 are selected from the group consisting of: deuterium, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms and combinations thereof; more preferably, at least one, at least two, at least three or all of R.sub.2, R.sub.3, R.sub.6 and R.sub.7 are selected from the group consisting of: deuterium, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, cyclopentyl, cyclohexyl, neopentyl, t-pentyl and combinations thereof; optionally, hydrogens in the above groups can be partially or fully deuterated.
17. The metal complex of claim 1, wherein L.sub.a is, at each occurrence identically or differently, selected from any one of the group consisting of the following: ##STR00122## ##STR00123## ##STR00124## ##STR00125## ##STR00126## ##STR00127## ##STR00128## ##STR00129## ##STR00130## ##STR00131## ##STR00132## ##STR00133## ##STR00134## ##STR00135## ##STR00136## ##STR00137## ##STR00138## ##STR00139## ##STR00140## ##STR00141## ##STR00142## ##STR00143## ##STR00144## ##STR00145## ##STR00146## ##STR00147## ##STR00148## ##STR00149## ##STR00150## ##STR00151## ##STR00152## ##STR00153## ##STR00154## ##STR00155## ##STR00156## ##STR00157## ##STR00158## ##STR00159## ##STR00160## ##STR00161## ##STR00162## ##STR00163## ##STR00164## ##STR00165## ##STR00166## ##STR00167## ##STR00168## ##STR00169## ##STR00170## ##STR00171## ##STR00172## ##STR00173## ##STR00174## ##STR00175## ##STR00176## ##STR00177## ##STR00178## ##STR00179## ##STR00180## ##STR00181## ##STR00182## ##STR00183## ##STR00184## ##STR00185## ##STR00186## ##STR00187## ##STR00188## ##STR00189## ##STR00190## ##STR00191## ##STR00192## ##STR00193## ##STR00194## ##STR00195## ##STR00196## ##STR00197## ##STR00198## ##STR00199## ##STR00200## ##STR00201## ##STR00202## ##STR00203## ##STR00204## ##STR00205## ##STR00206## ##STR00207## ##STR00208## ##STR00209## ##STR00210## ##STR00211## ##STR00212## ##STR00213## ##STR00214## ##STR00215## ##STR00216## ##STR00217## ##STR00218## ##STR00219## ##STR00220## ##STR00221## ##STR00222## ##STR00223## ##STR00224## ##STR00225## ##STR00226## ##STR00227## ##STR00228## ##STR00229## ##STR00230## ##STR00231## ##STR00232## ##STR00233## ##STR00234## ##STR00235## ##STR00236## ##STR00237## ##STR00238## ##STR00239## ##STR00240## ##STR00241## ##STR00242## ##STR00243## ##STR00244## ##STR00245## ##STR00246## ##STR00247## ##STR00248## ##STR00249## ##STR00250## ##STR00251## ##STR00252## ##STR00253## ##STR00254## ##STR00255## ##STR00256## ##STR00257## ##STR00258## ##STR00259## ##STR00260## ##STR00261## ##STR00262## ##STR00263## ##STR00264## ##STR00265## ##STR00266## ##STR00267## ##STR00268## ##STR00269## ##STR00270## ##STR00271## ##STR00272## ##STR00273## ##STR00274## ##STR00275## ##STR00276## ##STR00277## ##STR00278## ##STR00279## ##STR00280## ##STR00281## ##STR00282## ##STR00283## ##STR00284## ##STR00285## ##STR00286## ##STR00287## ##STR00288## ##STR00289## ##STR00290## ##STR00291## ##STR00292## ##STR00293## ##STR00294## ##STR00295## ##STR00296## ##STR00297## ##STR00298## ##STR00299## ##STR00300## ##STR00301## ##STR00302## ##STR00303## ##STR00304## ##STR00305## ##STR00306## ##STR00307## ##STR00308## ##STR00309## ##STR00310## ##STR00311## ##STR00312## ##STR00313## ##STR00314## ##STR00315## ##STR00316## ##STR00317## ##STR00318## ##STR00319## ##STR00320## ##STR00321## ##STR00322## ##STR00323## ##STR00324## ##STR00325## ##STR00326## ##STR00327## ##STR00328## ##STR00329## ##STR00330## ##STR00331## ##STR00332## ##STR00333## ##STR00334## ##STR00335## ##STR00336## ##STR00337## ##STR00338## ##STR00339## ##STR00340## ##STR00341## ##STR00342## ##STR00343## ##STR00344## ##STR00345## ##STR00346## ##STR00347## ##STR00348## ##STR00349## ##STR00350## ##STR00351## ##STR00352## ##STR00353## ##STR00354## ##STR00355## ##STR00356## ##STR00357## ##STR00358## ##STR00359## ##STR00360## ##STR00361## ##STR00362## ##STR00363## ##STR00364## ##STR00365## ##STR00366## ##STR00367## ##STR00368## ##STR00369## ##STR00370## ##STR00371## ##STR00372## ##STR00373## ##STR00374## ##STR00375## ##STR00376## ##STR00377## ##STR00378## ##STR00379## ##STR00380## ##STR00381## ##STR00382## ##STR00383## ##STR00384## ##STR00385## ##STR00386## ##STR00387## ##STR00388## ##STR00389## ##STR00390## ##STR00391## ##STR00392## ##STR00393## ##STR00394## ##STR00395## ##STR00396## ##STR00397## ##STR00398## ##STR00399## ##STR00400## ##STR00401## ##STR00402## ##STR00403## ##STR00404## ##STR00405## ##STR00406## ##STR00407## ##STR00408## ##STR00409## ##STR00410## ##STR00411## ##STR00412## ##STR00413## ##STR00414## ##STR00415## ##STR00416## ##STR00417## ##STR00418## ##STR00419## ##STR00420## ##STR00421## ##STR00422## ##STR00423## ##STR00424## ##STR00425## ##STR00426## ##STR00427## ##STR00428## ##STR00429## ##STR00430## ##STR00431## ##STR00432## ##STR00433## ##STR00434## ##STR00435## ##STR00436## ##STR00437## ##STR00438## ##STR00439## ##STR00440## ##STR00441## ##STR00442## ##STR00443## ##STR00444## ##STR00445## ##STR00446## ##STR00447## ##STR00448## ##STR00449## ##STR00450## ##STR00451## ##STR00452## ##STR00453## ##STR00454## ##STR00455## ##STR00456## ##STR00457## wherein optionally, hydrogens in the above structures of L.sub.a can be partially or fully deuterated.
18. The metal complex of claim 3, wherein L.sub.b is, at each occurrence identically or differently, selected from the group consisting of the following: ##STR00458## ##STR00459## ##STR00460## ##STR00461## ##STR00462## ##STR00463## ##STR00464## ##STR00465## ##STR00466## ##STR00467## ##STR00468## ##STR00469## ##STR00470## ##STR00471## ##STR00472## ##STR00473## ##STR00474## ##STR00475## ##STR00476## ##STR00477## ##STR00478## ##STR00479## ##STR00480## ##STR00481## ##STR00482## ##STR00483## ##STR00484## ##STR00485## ##STR00486## ##STR00487## ##STR00488## ##STR00489## ##STR00490## ##STR00491## ##STR00492## ##STR00493## ##STR00494## ##STR00495## ##STR00496## ##STR00497## ##STR00498## ##STR00499## ##STR00500## ##STR00501## ##STR00502## ##STR00503## ##STR00504## ##STR00505## ##STR00506## ##STR00507## ##STR00508## ##STR00509## ##STR00510## ##STR00511## ##STR00512## ##STR00513## ##STR00514## ##STR00515## ##STR00516## ##STR00517## ##STR00518## ##STR00519## ##STR00520## ##STR00521## ##STR00522## ##STR00523## wherein optionally, hydrogens in the structures of L.sub.b1 to L.sub.b329 can be partially or fully deuterated.
19. The metal complex of claim 3, wherein L.sub.c is, at each occurrence identically or differently, selected from the group consisting of the following. ##STR00524## ##STR00525## ##STR00526## ##STR00527## ##STR00528## ##STR00529## ##STR00530## ##STR00531## ##STR00532## ##STR00533## ##STR00534## ##STR00535## ##STR00536## ##STR00537## ##STR00538## ##STR00539## ##STR00540## ##STR00541## ##STR00542## ##STR00543## ##STR00544## ##STR00545## ##STR00546## ##STR00547## ##STR00548## ##STR00549## ##STR00550## ##STR00551## ##STR00552## ##STR00553## ##STR00554## ##STR00555## ##STR00556## ##STR00557## ##STR00558## ##STR00559## ##STR00560## ##STR00561## ##STR00562## ##STR00563## ##STR00564## ##STR00565## ##STR00566## ##STR00567## ##STR00568## ##STR00569## ##STR00570## ##STR00571## ##STR00572## ##STR00573## ##STR00574## ##STR00575## ##STR00576## ##STR00577## ##STR00578## ##STR00579## ##STR00580## ##STR00581## ##STR00582## ##STR00583## ##STR00584## ##STR00585## ##STR00586## ##STR00587## ##STR00588## ##STR00589## ##STR00590## ##STR00591## ##STR00592## ##STR00593## ##STR00594##
20. The metal complex of claim 1, wherein the metal complex has a structure of Ir(L.sub.a).sub.2(L.sub.b) or Ir(L.sub.a)(L.sub.b).sub.2 or Ir(L.sub.a).sub.3, wherein L.sub.a is, at each occurrence identically or differently, selected from any one, any two or any three of the group consisting of L.sub.a1-1 to L.sub.a1-497, L.sub.a2-1 to L.sub.a2-485, L.sub.a3-1 to L.sub.a3-485 and L.sub.a4-1 to L.sub.a4-226, and L.sub.b is selected from any one or any two of the group consisting of L.sub.b1 to L.sub.b329; or the metal complex has a structure of Ir(L.sub.a).sub.2(L.sub.c) or Ir(L.sub.a)(L.sub.c).sub.2, wherein L.sub.a is, at each occurrence identically or differently, selected from any one or any two of the group consisting of L.sub.a1-1 to L.sub.a1-497, L.sub.a2-1 to L.sub.a2-485, L.sub.a3-1 to L.sub.a3-485 and L.sub.a4-1 to L.sub.a4-226, and Le is selected from any one or any two of the group consisting of L.sub.c1 to L.sub.360; or the metal complex has a structure of Ir(L.sub.a)(L.sub.b)(L.sub.c), wherein L.sub.a is, at each occurrence identically or differently, selected from any one of the group consisting of L.sub.a1-1 to L.sub.a1-497, L.sub.a2-1 to L.sub.a2-185, L.sub.a3-1 to L.sub.a3-485 and L.sub.a4-1 to L.sub.a4-226, L.sub.b is selected from any one of the group consisting of L.sub.b1 to L.sub.b329, and L.sub.c is selected from any one of the group consisting of L.sub.c1 to L.sub.c360; preferably, the metal complex is selected from the group consisting of Metal Complex 1 to Metal Complex 2454 which are described as follows: Metal Complex 1 to Metal Complex 2344 each have a structure of Ir(L.sub.a)(L.sub.b).sub.2, wherein the two L.sub.b have the same structure or different structures, and L.sub.a and the two L.sub.b respectively correspond to the structures listed in the following table: TABLE-US-00005 Metal Metal Complex L.sub.a L.sub.b L.sub.b Complex L.sub.a L.sub.b L.sub.b 1 L.sub.a1-58 L.sub.b1 L.sub.b1 2 L.sub.a1-88 L.sub.b1 L.sub.b1 3 L.sub.a1-133 L.sub.b1 L.sub.b1 4 L.sub.a1-146 L.sub.b1 L.sub.b1 5 L.sub.a1-157 L.sub.b1 L.sub.b1 6 L.sub.a1-158 L.sub.b1 L.sub.b1 7 L.sub.a1-164 L.sub.b1 L.sub.b1 8 L.sub.a1-170 L.sub.b1 L.sub.b1 9 L.sub.a1-176 L.sub.b1 L.sub.b1 10 L.sub.a1-208 L.sub.b1 L.sub.b1 15 L.sub.a1-333 L.sub.b1 L.sub.b1 16 L.sub.a1-339 L.sub.b1 L.sub.b1 17 L.sub.a1-345 L.sub.b1 L.sub.b1 18 L.sub.a1-382 L.sub.b1 L.sub.b1 19 L.sub.a1-400 L.sub.b1 L.sub.b1 20 L.sub.a1-418 L.sub.b1 L.sub.b1 27 L.sub.a2-133 L.sub.b1 L.sub.b1 28 L.sub.a2-146 L.sub.b1 L.sub.b1 29 L.sub.a2-157 L.sub.b1 L.sub.b1 30 L.sub.a2-158 L.sub.b1 L.sub.b1 31 L.sub.a2-164 L.sub.b1 L.sub.b1 32 L.sub.a2-170 L.sub.b1 L.sub.b1 33 L.sub.a2-176 L.sub.b1 L.sub.b1 34 L.sub.a2-208 L.sub.b1 L.sub.b1 35 L.sub.a2-224 L.sub.b1 L.sub.b1 36 L.sub.a2-258 L.sub.b1 L.sub.b1 37 L.sub.a2-308 L.sub.b1 L.sub.b1 38 L.sub.a2-321 L.sub.b1 L.sub.b1 39 L.sub.a2-333 L.sub.b1 L.sub.b1 40 L.sub.a2-339 L.sub.b1 L.sub.b1 41 L.sub.a2-345 L.sub.b1 L.sub.b1 42 L.sub.a2-382 L.sub.b1 L.sub.b1 43 L.sub.a2-400 L.sub.b1 L.sub.b1 44 L.sub.a2-418 L.sub.b1 L.sub.b1 45 L.sub.a2-419 L.sub.b1 L.sub.b1 46 L.sub.a2-440 L.sub.b1 L.sub.b1 47 L.sub.a2-441 L.sub.b1 L.sub.b1 48 L.sub.a2-446 L.sub.b1 L.sub.b1 49 L.sub.a3-58 L.sub.b1 L.sub.b1 50 L.sub.a3-88 L.sub.b1 L.sub.b1 51 L.sub.a3-133 L.sub.b1 L.sub.b1 52 L.sub.a3-146 L.sub.b1 L.sub.b1 53 L.sub.a3-157 L.sub.b1 L.sub.b1 54 L.sub.a3-158 L.sub.b1 L.sub.b1 55 L.sub.a3-164 L.sub.b1 L.sub.b1 56 L.sub.a3-170 L.sub.b1 L.sub.b1 57 L.sub.a3-176 L.sub.b1 L.sub.b1 58 L.sub.a3-208 L.sub.b1 L.sub.b1 59 L.sub.a3-224 L.sub.b1 L.sub.b1 60 L.sub.a3-258 L.sub.b1 L.sub.b1 61 L.sub.a3-308 L.sub.b1 L.sub.b1 62 L.sub.a3-321 L.sub.b1 L.sub.b1 63 L.sub.a3-333 L.sub.b1 L.sub.b1 64 L.sub.a3-339 L.sub.b1 L.sub.b1 65 L.sub.a3-345 L.sub.b1 L.sub.b1 66 L.sub.a3-382 L.sub.b1 L.sub.b1 67 L.sub.a3-400 L.sub.b1 L.sub.b1 68 L.sub.a3-418 L.sub.b1 L.sub.b1 69 L.sub.a3-419 L.sub.b1 L.sub.b1 70 L.sub.a3-440 L.sub.b1 L.sub.b1 71 L.sub.a3-441 L.sub.b1 L.sub.b1 72 L.sub.a3-446 L.sub.b1 L.sub.b1 73 L.sub.a4-2 L.sub.b1 L.sub.b1 74 L.sub.a4-4 L.sub.b1 L.sub.b1 75 L.sub.a4-8 L.sub.b1 L.sub.b1 76 L.sub.a4-10 L.sub.b1 L.sub.b1 77 L.sub.a4-14 L.sub.b1 L.sub.b1 78 L.sub.a4-16 L.sub.b1 L.sub.b1 79 L.sub.a4-20 L.sub.b1 L.sub.b1 80 L.sub.a4-22 L.sub.b1 L.sub.b1 81 L.sub.a4-26 L.sub.b1 L.sub.b1 82 L.sub.a4-28 L.sub.b1 L.sub.b1 83 L.sub.a1-58 L.sub.b3 L.sub.b3 84 L.sub.a1-88 L.sub.b3 L.sub.b3 85 L.sub.a1-133 L.sub.b3 L.sub.b3 86 L.sub.a1-146 L.sub.b3 L.sub.b3 87 L.sub.a1-157 L.sub.b3 L.sub.b3 88 L.sub.a1-158 L.sub.b3 L.sub.b3 89 L.sub.a1-164 L.sub.b3 L.sub.b3 90 L.sub.a1-170 L.sub.b3 L.sub.b3 91 L.sub.a1-176 L.sub.b3 L.sub.b3 92 L.sub.a1-208 L.sub.b3 L.sub.b3 93 L.sub.a1-224 L.sub.b3 L.sub.b3 94 L.sub.a1-258 L.sub.b3 L.sub.b3 95 L.sub.a1-308 L.sub.b3 L.sub.b3 96 L.sub.a1-321 L.sub.b3 L.sub.b3 97 L.sub.a1-333 L.sub.b3 L.sub.b3 98 L.sub.a1-339 L.sub.b3 L.sub.b3 99 L.sub.a1-345 L.sub.b3 L.sub.b3 100 L.sub.a1-382 L.sub.b3 L.sub.b3 101 L.sub.a1-400 L.sub.b3 L.sub.b3 102 L.sub.a1-418 L.sub.b3 L.sub.b3 103 L.sub.a1-419 L.sub.b3 L.sub.b3 104 L.sub.a1-440 L.sub.b3 L.sub.b3 105 L.sub.a1-441 L.sub.b3 L.sub.b3 106 L.sub.a1-446 L.sub.b3 L.sub.b3 107 L.sub.a2-58 L.sub.b3 L.sub.b3 108 L.sub.a2-88 L.sub.b3 L.sub.b3 109 L.sub.a2-133 L.sub.b3 L.sub.b3 110 L.sub.a2-146 L.sub.b3 L.sub.b3 111 L.sub.a2-157 L.sub.b3 L.sub.b3 112 L.sub.a2-158 L.sub.b3 L.sub.b3 113 L.sub.a2-164 L.sub.b3 L.sub.b3 114 L.sub.a2-170 L.sub.b3 L.sub.b3 115 L.sub.a2-176 L.sub.b3 L.sub.b3 116 L.sub.a2-208 L.sub.b3 L.sub.b3 117 L.sub.a2-224 L.sub.b3 L.sub.b3 118 L.sub.a2-258 L.sub.b3 L.sub.b3 119 L.sub.a2-308 L.sub.b3 L.sub.b3 120 L.sub.a2-321 L.sub.b3 L.sub.b3 121 L.sub.a2-333 L.sub.b3 L.sub.b3 122 L.sub.a2-339 L.sub.b3 L.sub.b3 123 L.sub.a2-345 L.sub.b3 L.sub.b3 124 L.sub.a2-382 L.sub.b3 L.sub.b3 125 L.sub.a2-400 L.sub.b3 L.sub.b3 126 L.sub.a2-418 L.sub.b3 L.sub.b3 127 L.sub.a2-419 L.sub.b3 L.sub.b3 128 L.sub.a2-440 L.sub.b3 L.sub.b3 129 L.sub.a2-441 L.sub.b3 L.sub.b3 130 L.sub.a2-446 L.sub.b3 L.sub.b3 131 L.sub.a3-58 L.sub.b3 L.sub.b3 132 L.sub.a3-88 L.sub.b3 L.sub.b3 133 L.sub.a3-133 L.sub.b3 L.sub.b3 134 L.sub.a3-146 L.sub.b3 L.sub.b3 135 L.sub.a3-157 L.sub.b3 L.sub.b3 136 L.sub.a3-158 L.sub.b3 L.sub.b3 137 L.sub.a3-164 L.sub.b3 L.sub.b3 138 L.sub.a3-170 L.sub.b3 L.sub.b3 139 L.sub.a3-176 L.sub.b3 L.sub.b3 140 L.sub.a3-208 L.sub.b3 L.sub.b3 141 L.sub.a3-224 L.sub.b3 L.sub.b3 142 L.sub.a3-258 L.sub.b3 L.sub.b3 143 L.sub.a3-308 L.sub.b3 L.sub.b3 144 L.sub.a3-321 L.sub.b3 L.sub.b3 145 L.sub.a3-333 L.sub.b3 L.sub.b3 146 L.sub.a3-339 L.sub.b3 L.sub.b3 147 L.sub.a3-345 L.sub.b3 L.sub.b3 148 L.sub.a3-382 L.sub.b3 L.sub.b3 149 L.sub.a3-400 L.sub.b3 L.sub.b3 150 L.sub.a3-418 L.sub.b3 L.sub.b3 151 L.sub.a3-419 L.sub.b3 L.sub.b3 152 L.sub.a3-440 L.sub.b3 L.sub.b3 153 L.sub.a3-441 L.sub.b3 L.sub.b3 154 L.sub.a3-446 L.sub.b3 L.sub.b3 155 L.sub.a4-2 L.sub.b3 L.sub.b3 156 L.sub.a4-4 L.sub.b3 L.sub.b3 157 L.sub.a4-8 L.sub.b3 L.sub.b3 158 L.sub.a4-10 L.sub.b3 L.sub.b3 159 L.sub.a4-14 L.sub.b3 L.sub.b3 160 L.sub.a4-16 L.sub.b3 L.sub.b3 161 L.sub.a4-20 L.sub.b3 L.sub.b3 162 L.sub.a4-22 L.sub.b3 L.sub.b3 163 L.sub.a4-26 L.sub.b3 L.sub.b3 164 L.sub.a4-28 L.sub.b3 L.sub.b3 165 L.sub.a1-58 L.sub.b4 L.sub.b4 166 L.sub.a1-88 L.sub.b4 L.sub.b4 167 L.sub.a1-133 L.sub.b4 L.sub.b4 168 L.sub.a1-146 L.sub.b4 L.sub.b4 169 L.sub.a1-157 L.sub.b4 L.sub.b4 170 L.sub.a1-158 L.sub.b4 L.sub.b4 171 L.sub.a1-164 L.sub.b4 L.sub.b4 172 L.sub.a1-170 L.sub.b4 L.sub.b4 173 L.sub.a1-176 L.sub.b4 L.sub.b4 174 L.sub.a1-208 L.sub.b4 L.sub.b4 175 L.sub.a1-224 L.sub.b4 L.sub.b4 176 L.sub.a1-258 L.sub.b4 L.sub.b4 177 L.sub.a1-308 L.sub.b4 L.sub.b4 178 L.sub.a1-321 L.sub.b4 L.sub.b4 179 L.sub.a1-333 L.sub.b4 L.sub.b4 180 L.sub.a1-339 L.sub.b4 L.sub.b4 181 L.sub.a1-345 L.sub.b4 L.sub.b4 182 L.sub.a1-382 L.sub.b4 L.sub.b4 183 L.sub.a1-400 L.sub.b4 L.sub.b4 184 L.sub.a1-418 L.sub.b4 L.sub.b4 185 L.sub.a1-419 L.sub.b4 L.sub.b4 186 L.sub.a1-440 L.sub.b4 L.sub.b4 187 L.sub.a1-441 L.sub.b4 L.sub.b4 188 L.sub.a1-446 L.sub.b4 L.sub.b4 189 L.sub.a2-58 L.sub.b4 L.sub.b4 190 L.sub.a2-88 L.sub.b4 L.sub.b4 191 L.sub.a2-133 L.sub.b4 L.sub.b4 192 L.sub.a2-146 L.sub.b4 L.sub.b4 193 L.sub.a2-157 L.sub.b4 L.sub.b4 194 L.sub.a2-158 L.sub.b4 L.sub.b4 195 L.sub.a2-164 L.sub.b4 L.sub.b4 196 L.sub.a2-170 L.sub.b4 L.sub.b4 197 L.sub.a2-176 L.sub.b4 L.sub.b4 198 L.sub.a2-208 L.sub.b4 L.sub.b4 199 L.sub.a2-224 L.sub.b4 L.sub.b4 200 L.sub.a2-258 L.sub.b4 L.sub.b4 201 L.sub.a2-308 L.sub.b4 L.sub.b4 202 L.sub.a2-321 L.sub.b4 L.sub.b4 203 L.sub.a2-333 L.sub.b4 L.sub.b4 204 L.sub.a2-339 L.sub.b4 L.sub.b4 205 L.sub.a2-345 L.sub.b4 L.sub.b4 206 L.sub.a2-382 L.sub.b4 L.sub.b4 207 L.sub.a2-400 L.sub.b4 L.sub.b4 208 L.sub.a2-418 L.sub.b4 L.sub.b4 209 L.sub.a2-419 L.sub.b4 L.sub.b4 210 L.sub.a2-440 L.sub.b4 L.sub.b4 211 L.sub.a2-441 L.sub.b4 L.sub.b4 212 L.sub.a2-446 L.sub.b4 L.sub.b4 213 L.sub.a3-58 L.sub.b4 L.sub.b4 214 L.sub.a3-88 L.sub.b4 L.sub.b4 215 L.sub.a3-133 L.sub.b4 L.sub.b4 216 L.sub.a3-146 L.sub.b4 L.sub.b4 217 L.sub.a3-157 L.sub.b4 L.sub.b4 218 L.sub.a3-158 L.sub.b4 L.sub.b4 219 L.sub.a3-164 L.sub.b4 L.sub.b4 220 L.sub.a3-170 L.sub.b4 L.sub.b4 221 L.sub.a3-176 L.sub.b4 L.sub.b4 222 L.sub.a3-208 L.sub.b4 L.sub.b4 223 L.sub.a3-224 L.sub.b4 L.sub.b4 224 L.sub.a3-258 L.sub.b4 L.sub.b4 225 L.sub.a3-308 L.sub.b4 L.sub.b4 226 L.sub.a3-321 L.sub.b4 L.sub.b4 227 L.sub.a3-333 L.sub.b4 L.sub.b4 228 L.sub.a3-339 L.sub.b4 L.sub.b4 229 L.sub.a3-345 L.sub.b4 L.sub.b4 230 L.sub.a3-382 L.sub.b4 L.sub.b4 231 L.sub.a3-400 L.sub.b4 L.sub.b4 232 L.sub.a3-418 L.sub.b4 L.sub.b4 233 L.sub.a3-419 L.sub.b4 L.sub.b4 234 L.sub.a3-440 L.sub.b4 L.sub.b4 235 L.sub.a3-441 L.sub.b4 L.sub.b4 236 L.sub.a3-446 L.sub.b4 L.sub.b4 237 L.sub.a4-2 L.sub.b8 L.sub.b8 238 L.sub.a4-4 L.sub.b8 L.sub.b8 239 L.sub.a4-8 L.sub.b8 L.sub.b8 240 L.sub.a4-10 L.sub.b8 L.sub.b8 241 L.sub.a4-14 L.sub.b8 L.sub.b8 242 L.sub.a4-16 L.sub.b8 L.sub.b8 243 L.sub.a4-20 L.sub.b8 L.sub.b8 244 L.sub.a4-22 L.sub.b8 L.sub.b8 245 L.sub.a4-26 L.sub.b8 L.sub.b8 246 L.sub.a4-28 L.sub.b8 L.sub.b8 247 L.sub.a1-58 L.sub.b8 L.sub.b8 248 L.sub.a1-88 L.sub.b8 L.sub.b8 249 L.sub.a1-133 L.sub.b8 L.sub.b8 250 L.sub.a1-146 L.sub.b8 L.sub.b8 251 L.sub.a1-157 L.sub.b8 L.sub.b8 252 L.sub.a1-158 L.sub.b8 L.sub.b8 253 L.sub.a1-164 L.sub.b8 L.sub.b8 254 L.sub.a1-170 L.sub.b8 L.sub.b8 255 L.sub.a1-176 L.sub.b8 L.sub.b8 256 L.sub.a1-208 L.sub.b8 L.sub.b8 257 L.sub.a1-224 L.sub.b8 L.sub.b8 258 L.sub.a1-258 L.sub.b8 L.sub.b8 259 L.sub.a1-308 L.sub.b8 L.sub.b8 260 L.sub.a1-321 L.sub.b8 L.sub.b8 261 L.sub.a1-333 L.sub.b8 L.sub.b8 262 L.sub.a1-339 L.sub.b8 L.sub.b8 263 L.sub.a1-345 L.sub.b8 L.sub.b8 264 L.sub.a1-382 L.sub.b8 L.sub.b8 265 L.sub.a1-400 L.sub.b8 L.sub.b8 266 L.sub.a1-418 L.sub.b8 L.sub.b8 267 L.sub.a1-419 L.sub.b8 L.sub.b8 268 L.sub.a1-440 L.sub.b8 L.sub.b8 269 L.sub.a1-441 L.sub.b8 L.sub.b8 270 L.sub.a1-446 L.sub.b8 L.sub.b8 271 L.sub.a2-58 L.sub.b8 L.sub.b8 272 L.sub.a2-88 L.sub.b8 L.sub.b8 273 L.sub.a2-133 L.sub.b8 L.sub.b8 274 L.sub.a2-146 L.sub.b8 L.sub.b8 275 L.sub.a2-157 L.sub.b8 L.sub.b8 276 L.sub.a2-158 L.sub.b8 L.sub.b8 277 L.sub.a2-164 L.sub.b8 L.sub.b8 278 L.sub.a2-170 L.sub.b8 L.sub.b8 279 L.sub.a2-176 L.sub.b8 L.sub.b8 280 L.sub.a2-208 L.sub.b8 L.sub.b8 281 L.sub.a2-224 L.sub.b8 L.sub.b8 282 L.sub.a2-258 L.sub.b8 L.sub.b8 283 L.sub.a2-308 L.sub.b8 L.sub.b8 284 L.sub.a2-321 L.sub.b8 L.sub.b8 285 L.sub.a2-333 L.sub.b8 L.sub.b8 286 L.sub.a2-339 L.sub.b8 L.sub.b8 287 L.sub.a2-345 L.sub.b8 L.sub.b8 288 L.sub.a2-382 L.sub.b8 L.sub.b8 289 L.sub.a2-400 L.sub.b8 L.sub.b8 290 L.sub.a2-418 L.sub.b8 L.sub.b8 291 L.sub.a2-419 L.sub.b8 L.sub.b8 292 L.sub.a2-440 L.sub.b8 L.sub.b8 293 L.sub.a2-441 L.sub.b8 L.sub.b8 294 L.sub.a2-446 L.sub.b8 L.sub.b8 295 L.sub.a3-58 L.sub.b8 L.sub.b8 296 L.sub.a3-88 L.sub.b8 L.sub.b8 297 L.sub.a3-133 L.sub.b8 L.sub.b8 298 L.sub.a3-146 L.sub.b8 L.sub.b8 299 L.sub.a3-157 L.sub.b8 L.sub.b8 300 L.sub.a3-158 L.sub.b8 L.sub.b8 301 L.sub.a3-164 L.sub.b8 L.sub.b8 302 L.sub.a3-170 L.sub.b8 L.sub.b8 303 L.sub.a3-176 L.sub.b8 L.sub.b8 304 L.sub.a3-208 L.sub.b8 L.sub.b8 305 L.sub.a3-224 L.sub.b8 L.sub.b8 306 L.sub.a3-258 L.sub.b8 L.sub.b8 307 L.sub.a3-308 L.sub.b8 L.sub.b8 308 L.sub.a3-321 L.sub.b8 L.sub.b8 309 L.sub.a3-333 L.sub.b8 L.sub.b8 310 L.sub.a3-339 L.sub.b8 L.sub.b8 311 L.sub.a3-345 L.sub.b8 L.sub.b8 312 L.sub.a3-382 L.sub.b8 L.sub.b8 313 L.sub.a3-400 L.sub.b8 L.sub.b8 314 L.sub.a3-418 L.sub.b8 L.sub.b8 315 L.sub.a3-419 L.sub.b8 L.sub.b8 316 L.sub.a3-440 L.sub.b8 L.sub.b8 317 L.sub.a3-441 L.sub.b8 L.sub.b8 318 L.sub.a3-446 L.sub.b8 L.sub.b8 319 L.sub.a4-2 L.sub.b8 L.sub.b8 320 L.sub.a4-4 L.sub.b8 L.sub.b8 321 L.sub.a4-8 L.sub.b8 L.sub.b8 322 L.sub.a4-10 L.sub.b8 L.sub.b8 323 L.sub.a4-14 L.sub.b8 L.sub.b8 324 L.sub.a4-16 L.sub.b8 L.sub.b8 325 L.sub.a4-20 L.sub.b8 L.sub.b8 326 L.sub.a4-22 L.sub.b8 L.sub.b8 327 L.sub.a4-26 L.sub.b8 L.sub.b8 328 L.sub.a4-28 L.sub.b8 L.sub.b8 329 L.sub.a1-58 L.sub.b10 L.sub.b10 330 L.sub.a1-88 L.sub.b10 L.sub.b10 331 L.sub.a1-133 L.sub.b10 L.sub.b10 332 L.sub.a1-146 L.sub.b10 L.sub.b10 333 L.sub.a1-157 L.sub.b10 L.sub.b10 334 L.sub.a1-158 L.sub.b10 L.sub.b10 335 L.sub.a1-164 L.sub.b10 L.sub.b10 336 L.sub.a1-170 L.sub.b10 L.sub.b10 337 L.sub.a1-176 L.sub.b10 L.sub.b10 338 L.sub.a1-208 L.sub.b10 L.sub.b10 339 L.sub.a1-224 L.sub.b10 L.sub.b10 340 L.sub.a1-258 L.sub.b10 L.sub.b10 341 L.sub.a1-308 L.sub.b10 L.sub.b10 342 L.sub.a1-321 L.sub.b10 L.sub.b10 343 L.sub.a1-333 L.sub.b10 L.sub.b10 344 L.sub.a1-339 L.sub.b10 L.sub.b10 345 L.sub.a1-345 L.sub.b10 L.sub.b10 346 L.sub.a1-382 L.sub.b10 L.sub.b10 347 L.sub.a1-400 L.sub.b10 L.sub.b10 348 L.sub.a1-418 L.sub.b10 L.sub.b10 349 L.sub.a1-419 L.sub.b10 L.sub.b10 350 L.sub.a1-440 L.sub.b10 L.sub.b10 351 L.sub.a1-441 L.sub.b10 L.sub.b10 352 L.sub.a1-446 L.sub.b10 L.sub.b10 353 L.sub.a2-58 L.sub.b10 L.sub.b10 354 L.sub.a2-88 L.sub.b10 L.sub.b10 355 L.sub.a2-133 L.sub.b10 L.sub.b10 356 L.sub.a2-146 L.sub.b10 L.sub.b10 357 L.sub.a2-157 L.sub.b10 L.sub.b10 358 L.sub.a2-158 L.sub.b10 L.sub.b10 359 L.sub.a2-164 L.sub.b10 L.sub.b10 360 L.sub.a2-170 L.sub.b10 L.sub.b10 361 L.sub.a2-176 L.sub.b10 L.sub.b10 362 L.sub.a2-208 L.sub.b10 L.sub.b10 363 L.sub.a2-224 L.sub.b10 L.sub.b10 364 L.sub.a2-258 L.sub.b10 L.sub.b10 365 L.sub.a2-308 L.sub.b10 L.sub.b10 366 L.sub.a2-321 L.sub.b10 L.sub.b10 367 L.sub.a2-333 L.sub.b10 L.sub.b10 368 L.sub.a2-339 L.sub.b10 L.sub.b10 369 L.sub.a2-345 L.sub.b10 L.sub.b10 370 L.sub.a2-382 L.sub.b10 L.sub.b10 371 L.sub.a2-400 L.sub.b10 L.sub.b10 372 L.sub.a2-418 L.sub.b10 L.sub.b10 373 L.sub.a2-419 L.sub.b10 L.sub.b10 374 L.sub.a2-440 L.sub.b10 L.sub.b10 375 L.sub.a2-441 L.sub.b10 L.sub.b10 376 L.sub.a2-446 L.sub.b10 L.sub.b10 377 L.sub.a3-58 L.sub.b10 L.sub.b10 378 L.sub.a3-88 L.sub.b10 L.sub.b10 379 L.sub.a3-133 L.sub.b10 L.sub.b10 380 L.sub.a3-146 L.sub.b10 L.sub.b10 381 L.sub.a3-157 L.sub.b10 L.sub.b10 382 L.sub.a3-158 L.sub.b10 L.sub.b10 383 L.sub.a3-164 L.sub.b10 L.sub.b10 384 L.sub.a3-170 L.sub.b10 L.sub.b10 385 L.sub.a3-176 L.sub.b10 L.sub.b10 386 L.sub.a3-208 L.sub.b10 L.sub.b10 387 L.sub.a3-224 L.sub.b10 L.sub.b10 388 L.sub.a3-258 L.sub.b10 L.sub.b10 389 L.sub.a3-308 L.sub.b10 L.sub.b10 390 L.sub.a3-321 L.sub.b10 L.sub.b10 391 L.sub.a3-333 L.sub.b10 L.sub.b10 392 L.sub.a3-339 L.sub.b10 L.sub.b10 393 L.sub.a3-345 L.sub.b10 L.sub.b10 394 L.sub.a3-382 L.sub.b10 L.sub.b10 395 L.sub.a3-400 L.sub.b10 L.sub.b10 396 L.sub.a3-418 L.sub.b10 L.sub.b10 397 L.sub.a3-419 L.sub.b10 L.sub.b10 398 L.sub.a3-440 L.sub.b10 L.sub.b10 399 L.sub.a3-441 L.sub.b10 L.sub.b10 400 L.sub.a3-446 L.sub.b10 L.sub.b10 401 L.sub.a4-2 L.sub.b10 L.sub.b10 402 L.sub.a4-4 L.sub.b10 L.sub.b10 403 L.sub.a4-8 L.sub.b10 L.sub.b10 404 L.sub.a4-10 L.sub.b10 L.sub.b10 405 L.sub.a4-14 L.sub.b10 L.sub.b10 406 L.sub.a4-16 L.sub.b10 L.sub.b10 407 L.sub.a4-20 L.sub.b10 L.sub.b10 408 L.sub.a4-22 L.sub.b10 L.sub.b10 409 L.sub.a4-26 L.sub.b10 L.sub.b10 410 L.sub.a4-28 L.sub.b10 L.sub.b10 411 L.sub.a1-58 L.sub.b12 L.sub.b12 412 L.sub.a1-88 L.sub.b12 L.sub.b12 413 L.sub.a1-133 L.sub.b12 L.sub.b12 414 L.sub.a1-146 L.sub.b12 L.sub.b12 415 L.sub.a1-157 L.sub.b12 L.sub.b12 416 L.sub.a1-158 L.sub.b12 L.sub.b12 417 L.sub.a1-164 L.sub.b12 L.sub.b12 418 L.sub.a1-170 L.sub.b12 L.sub.b12 419 L.sub.a1-176 L.sub.b12 L.sub.b12 420 L.sub.a1-208 L.sub.b12 L.sub.b12 421 L.sub.a1-224 L.sub.b12 L.sub.b12 422 L.sub.a1-258 L.sub.b12 L.sub.b12 423 L.sub.a1-308 L.sub.b12 L.sub.b12 424 L.sub.a1-321 L.sub.b12 L.sub.b12 425 L.sub.a1-333 L.sub.b12 L.sub.b12 426 L.sub.a1-339 L.sub.b12 L.sub.b12 427 L.sub.a1-345 L.sub.b12 L.sub.b12 428 L.sub.a1-382 L.sub.b12 L.sub.b12 429 L.sub.a1-400 L.sub.b12 L.sub.b12 430 L.sub.a1-418 L.sub.b12 L.sub.b12 431 L.sub.a1-419 L.sub.b12 L.sub.b12 432 L.sub.a1-440 L.sub.b12 L.sub.b12 433 L.sub.a1-441 L.sub.b12 L.sub.b12 434 L.sub.a1-446 L.sub.b12 L.sub.b12 435 L.sub.a2-58 L.sub.b12 L.sub.b12 436 L.sub.a2-88 L.sub.b12 L.sub.b12 437 L.sub.a2-133 L.sub.b12 L.sub.b12 438 L.sub.a2-146 L.sub.b12 L.sub.b12 439 L.sub.a2-157 L.sub.b12 L.sub.b12 440 L.sub.a2-158 L.sub.b12 L.sub.b12 441 L.sub.a2-164 L.sub.b12 L.sub.b12 442 L.sub.a2-170 L.sub.b12 L.sub.b12 443 L.sub.a2-176 L.sub.b12 L.sub.b12 444 L.sub.a2-208 L.sub.b12 L.sub.b12 445 L.sub.a2-224 L.sub.b12 L.sub.b12 446 L.sub.a2-258 L.sub.b12 L.sub.b12 447 L.sub.a2-308 L.sub.b12 L.sub.b12 448 L.sub.a2-321 L.sub.b12 L.sub.b12 449 L.sub.a2-333 L.sub.b12 L.sub.b12 450 L.sub.a2-339 L.sub.b12 L.sub.b12 451 L.sub.a2-345 L.sub.b12 L.sub.b12 452 L.sub.a2-382 L.sub.b12 L.sub.b12 453 L.sub.a2-400 L.sub.b12 L.sub.b12 454 L.sub.a2-418 L.sub.b12 L.sub.b12 455 L.sub.a2-419 L.sub.b12 L.sub.b12 456 L.sub.a2-440 L.sub.b12 L.sub.b12 457 L.sub.a2-441 L.sub.b12 L.sub.b12 458 L.sub.a2-446 L.sub.b12 L.sub.b12 459 L.sub.a3-58 L.sub.b12 L.sub.b12 460 L.sub.a3-88 L.sub.b12 L.sub.b12 461 L.sub.a3-133 L.sub.b12 L.sub.b12 462 L.sub.a3-146 L.sub.b12 L.sub.b12 463 L.sub.a3-157 L.sub.b12 L.sub.b12 464 L.sub.a3-158 L.sub.b12 L.sub.b12 465 L.sub.a3-164 L.sub.b12 L.sub.b12 466 L.sub.a3-170 L.sub.b12 L.sub.b12 467 L.sub.a3-176 L.sub.b12 L.sub.b12 468 L.sub.a3-208 L.sub.b12 L.sub.b12 469 L.sub.a3-224 L.sub.b12 L.sub.b12 470 L.sub.a3-258 L.sub.b12 L.sub.b12 471 L.sub.a3-308 L.sub.b12 L.sub.b12 472 L.sub.a3-321 L.sub.b12 L.sub.b12 473 L.sub.a3-333 L.sub.b12 L.sub.b12 474 L.sub.a3-339 L.sub.b12 L.sub.b12 475 L.sub.a3-345 L.sub.b12 L.sub.b12 476 L.sub.a3-382 L.sub.b12 L.sub.b12 477 L.sub.a3-400 L.sub.b12 L.sub.b12 478 L.sub.a3-418 L.sub.b12 L.sub.b12 479 L.sub.a3-419 L.sub.b12 L.sub.b12 480 L.sub.a3-440 L.sub.b12 L.sub.b12 481 L.sub.a3-441 L.sub.b12 L.sub.b12 482 L.sub.a3-446 L.sub.b12 L.sub.b12 483 L.sub.a4-2 L.sub.b12 L.sub.b12 484 L.sub.a4-4 L.sub.b12 L.sub.b12 485 L.sub.a4-8 L.sub.b12 L.sub.b12 486 L.sub.a4-10 L.sub.b12 L.sub.b12 487 L.sub.a4-14 L.sub.b12 L.sub.b12 488 L.sub.a4-16 L.sub.b12 L.sub.b12 489 L.sub.a4-20 L.sub.b12 L.sub.b12 490 L.sub.a4-22 L.sub.b12 L.sub.b12 491 L.sub.a4-26 L.sub.b12 L.sub.b12 492 L.sub.a4-28 L.sub.b12 L.sub.b12 493 L.sub.a1-58 L.sub.b13 L.sub.b13 494 L.sub.a1-88 L.sub.b13 L.sub.b13 495 L.sub.a1-133 L.sub.b13 L.sub.b13 496 L.sub.a1-146 L.sub.b13 L.sub.b13 497 L.sub.a1-157 L.sub.b13 L.sub.b13 498 L.sub.a1-158 L.sub.b13 L.sub.b13 499 L.sub.a1-164 L.sub.b13 L.sub.b13 500 L.sub.a1-170 L.sub.b13 L.sub.b13 501 L.sub.a1-176 L.sub.b13 L.sub.b13 502 L.sub.a1-208 L.sub.b13 L.sub.b13 503 L.sub.a1-224 L.sub.b13 L.sub.b13 504 L.sub.a1-258 L.sub.b13 L.sub.b13 505 L.sub.a1-308 L.sub.b13 L.sub.b13 506 L.sub.a1-321 L.sub.b13 L.sub.b13 507 L.sub.a1-333 L.sub.b13 L.sub.b13 508 L.sub.a1-339 L.sub.b13 L.sub.b13 509 L.sub.a1-345 L.sub.b13 L.sub.b13 510 L.sub.a1-382 L.sub.b13 L.sub.b13 511 L.sub.a1-400 L.sub.b13 L.sub.b13 512 L.sub.a1-418 L.sub.b13 L.sub.b13 513 L.sub.a1-419 L.sub.b13 L.sub.b13 514 L.sub.a1-440 L.sub.b13 L.sub.b13 515 L.sub.a1-441 L.sub.b13 L.sub.b13 516 L.sub.a1-446 L.sub.b13 L.sub.b13 517 L.sub.a2-58 L.sub.b13 L.sub.b13 518 L.sub.a2-88 L.sub.b13 L.sub.b13 519 L.sub.a2-133 L.sub.b13 L.sub.b13 520 L.sub.a2-146 L.sub.b13 L.sub.b13 521 L.sub.a2-157 L.sub.b13 L.sub.b13 522 L.sub.a2-158 L.sub.b13 L.sub.b13 523 L.sub.a2-164 L.sub.b13 L.sub.b13 524 L.sub.a2-170 L.sub.b13 L.sub.b13 525 L.sub.a2-176 L.sub.b13 L.sub.b13 526 L.sub.a2-208 L.sub.b13 L.sub.b13 527 L.sub.a2-224 L.sub.b13 L.sub.b13 528 L.sub.a2-258 L.sub.b13 L.sub.b13 529 L.sub.a2-308 L.sub.b13 L.sub.b13 530 L.sub.a2-321 L.sub.b13 L.sub.b13 531 L.sub.a2-333 L.sub.b13 L.sub.b13 532 L.sub.a2-339 L.sub.b13 L.sub.b13 533 L.sub.a2-345 L.sub.b13 L.sub.b13 534 L.sub.a2-382 L.sub.b13 L.sub.b13 535 L.sub.a2-400 L.sub.b13 L.sub.b13 536 L.sub.a2-418 L.sub.b13 L.sub.b13 537 L.sub.a2-419 L.sub.b13 L.sub.b13 538 L.sub.a2-440 L.sub.b13 L.sub.b13 539 L.sub.a2-441 L.sub.b13 L.sub.b13 540 L.sub.a2-446 L.sub.b13 L.sub.b13 541 L.sub.a3-58 L.sub.b13 L.sub.b13 542 L.sub.a3-88 L.sub.b13 L.sub.b13 543 L.sub.a3-133 L.sub.b13 L.sub.b13 544 L.sub.a3-146 L.sub.b13 L.sub.b13 545 L.sub.a3-157 L.sub.b13 L.sub.b13 546 L.sub.a3-158 L.sub.b13 L.sub.b13 547 L.sub.a3-164 L.sub.b13 L.sub.b13 548 L.sub.a3-170 L.sub.b13 L.sub.b13 549 L.sub.a3-176 L.sub.b13 L.sub.b13 550 L.sub.a3-208 L.sub.b13 L.sub.b13 551 L.sub.a3-224 L.sub.b13 L.sub.b13 552 L.sub.a3-258 L.sub.b13 L.sub.b13 553 L.sub.a3-308 L.sub.b13 L.sub.b13 554 L.sub.a3-321 L.sub.b13 L.sub.b13 555 L.sub.a3-333 L.sub.b13 L.sub.b13 556 L.sub.a3-339 L.sub.b13 L.sub.b13 557 L.sub.a3-345 L.sub.b13 L.sub.b13 558 L.sub.a3-382 L.sub.b13 L.sub.b13 559 L.sub.a3-400 L.sub.b13 L.sub.b13 560 L.sub.a3-418 L.sub.b13 L.sub.b13 561 L.sub.a3-419 L.sub.b13 L.sub.b13 562 L.sub.a3-440 L.sub.b13 L.sub.b13 563 L.sub.a3-441 L.sub.b13 L.sub.b13 564 L.sub.a3-446 L.sub.b13 L.sub.b13 565 L.sub.a4-2 L.sub.b13 L.sub.b13 566 L.sub.a4-4 L.sub.b13 L.sub.b13 567 L.sub.a4-8 L.sub.b13 L.sub.b13 568 L.sub.a4-10 L.sub.b13 L.sub.b13 569 L.sub.a4-14 L.sub.b13 L.sub.b13 570 L.sub.a4-16 L.sub.b13 L.sub.b13 571 L.sub.a4-20 L.sub.b13 L.sub.b13 572 L.sub.a4-22 L.sub.b13 L.sub.b13 573 L.sub.a4-26 L.sub.b13 L.sub.b13 574 L.sub.a4-28 L.sub.b13 L.sub.b13 575 L.sub.a1-58 L.sub.b17 L.sub.b17 576 L.sub.a1-88 L.sub.b17 L.sub.b17 577 L.sub.a1-133 L.sub.b17 L.sub.b17 578 L.sub.a1-146 L.sub.b17 L.sub.b17 579 L.sub.a1-157 L.sub.b17 L.sub.b17 580 L.sub.a1-158 L.sub.b17 L.sub.b17 581 L.sub.a1-164 L.sub.b17 L.sub.b17 582 L.sub.a1-170 L.sub.b17 L.sub.b17 583 L.sub.a1-176 L.sub.b17 L.sub.b17 584 L.sub.a1-208 L.sub.b17 L.sub.b17 585 L.sub.a1-224 L.sub.b17 L.sub.b17 586 L.sub.a1-258 L.sub.b17 L.sub.b17 587 L.sub.a1-308 L.sub.b17 L.sub.b17 588 L.sub.a1-321 L.sub.b17 L.sub.b17 589 L.sub.a1-333 L.sub.b17 L.sub.b17 590 L.sub.a1-339 L.sub.b17 L.sub.b17 591 L.sub.a1-345 L.sub.b17 L.sub.b17 592 L.sub.a1-382 L.sub.b17 L.sub.b17 593 L.sub.a1-400 L.sub.b17 L.sub.b17 594 L.sub.a1-418 L.sub.b17 L.sub.b17 595 L.sub.a1-419 L.sub.b17 L.sub.b17 596 L.sub.a1-440 L.sub.b17 L.sub.b17 597 L.sub.a1-441 L.sub.b17 L.sub.b17 598 L.sub.a1-446 L.sub.b17 L.sub.b17 599 L.sub.a2-58 L.sub.b17 L.sub.b17 600 L.sub.a2-88 L.sub.b17 L.sub.b17 601 L.sub.a2-133 L.sub.b17 L.sub.b17 602 L.sub.a2-146 L.sub.b17 L.sub.b17 603 L.sub.a2-157 L.sub.b17 L.sub.b17 604 L.sub.a2-158 L.sub.b17 L.sub.b17 605 L.sub.a2-164 L.sub.b17 L.sub.b17 606 L.sub.a2-170 L.sub.b17 L.sub.b17 607 L.sub.a2-176 L.sub.b17 L.sub.b17 608 L.sub.a2-208 L.sub.b17 L.sub.b17 609 L.sub.a2-224 L.sub.b17 L.sub.b17 610 L.sub.a2-258 L.sub.b17 L.sub.b17 611 L.sub.a2-308 L.sub.b17 L.sub.b17 612 L.sub.a2-321 L.sub.b17 L.sub.b17 613 L.sub.a2-333 L.sub.b17 L.sub.b17 614 L.sub.a2-339 L.sub.b17 L.sub.b17 615 L.sub.a2-345 L.sub.b17 L.sub.b17 616 L.sub.a2-382 L.sub.b17 L.sub.b17 617 L.sub.a2-400 L.sub.b17 L.sub.b17 618 L.sub.a2-418 L.sub.b17 L.sub.b17 619 L.sub.a2-419 L.sub.b17 L.sub.b17 620 L.sub.a2-440 L.sub.b17 L.sub.b17 621 L.sub.a2-441 L.sub.b17 L.sub.b17 622 L.sub.a2-446 L.sub.b17 L.sub.b17 623 L.sub.a3-58 L.sub.b17 L.sub.b17 624 L.sub.a3-88 L.sub.b17 L.sub.b17 625 L.sub.a3-133 L.sub.b17 L.sub.b17 626 L.sub.a3-146 L.sub.b17 L.sub.b17 627 L.sub.a3-157 L.sub.b17 L.sub.b17 628 L.sub.a3-158 L.sub.b17 L.sub.b17 629 L.sub.a3-164 L.sub.b17 L.sub.b17 630 L.sub.a3-170 L.sub.b17 L.sub.b17 631 L.sub.a3-176 L.sub.b17 L.sub.b17 632 L.sub.a3-208 L.sub.b17 L.sub.b17 633 L.sub.a3-224 L.sub.b17 L.sub.b17 634 L.sub.a3-258 L.sub.b17 L.sub.b17 635 L.sub.a3-308 L.sub.b17 L.sub.b17 636 L.sub.a3-321 L.sub.b17 L.sub.b17 637 L.sub.a3-333 L.sub.b17 L.sub.b17 638 L.sub.a3-339 L.sub.b17 L.sub.b17 639 L.sub.a3-345 L.sub.b17 L.sub.b17 640 L.sub.a3-382 L.sub.b17 L.sub.b17 641 L.sub.a3-400 L.sub.b17 L.sub.b17 642 L.sub.a3-418 L.sub.b17 L.sub.b17 643 L.sub.a3-419 L.sub.b17 L.sub.b17 644 L.sub.a3-440 L.sub.b17 L.sub.b17 645 L.sub.a3-441 L.sub.b17 L.sub.b17 646 L.sub.a3-446 L.sub.b17 L.sub.b17 647 L.sub.a4-2 L.sub.b17 L.sub.b17 648 L.sub.a4-4 L.sub.b17 L.sub.b17 649 L.sub.a4-8 L.sub.b17 L.sub.b17 650 L.sub.a4-10 L.sub.b17 L.sub.b17 651 L.sub.a4-14 L.sub.b17 L.sub.b17 652 L.sub.a4-16 L.sub.b17 L.sub.b17 653 L.sub.a4-20 L.sub.b17 L.sub.b17 654 L.sub.a4-22 L.sub.b17 L.sub.b17 655 L.sub.a4-26 L.sub.b17 L.sub.b17 656 L.sub.a4-28 L.sub.b17 L.sub.b17 657 L.sub.a1-58 L.sub.b30 L.sub.b30 658 L.sub.a1-88 L.sub.b30 L.sub.b30 659 L.sub.a1-133 L.sub.b30 L.sub.b30 660 L.sub.a1-146 L.sub.b30 L.sub.b30 661 L.sub.a1-157 L.sub.b30 L.sub.b30 662 L.sub.a1-158 L.sub.b30 L.sub.b30 663 L.sub.a1-164 L.sub.b30 L.sub.b30 664 L.sub.a1-170 L.sub.b30 L.sub.b30 665 L.sub.a1-176 L.sub.b30 L.sub.b30 666 L.sub.a1-208 L.sub.b30 L.sub.b30 667 L.sub.a1-224 L.sub.b30 L.sub.b30 668 L.sub.a1-258 L.sub.b30 L.sub.b30 669 L.sub.a1-308 L.sub.b30 L.sub.b30 670 L.sub.a1-321 L.sub.b30 L.sub.b30 671 L.sub.a1-333 L.sub.b30 L.sub.b30 672 L.sub.a1-339 L.sub.b30 L.sub.b30 673 L.sub.a1-345 L.sub.b30 L.sub.b30 674 L.sub.a1-382 L.sub.b30 L.sub.b30 675 L.sub.a1-400 L.sub.b30 L.sub.b30 676 L.sub.a1-418 L.sub.b30 L.sub.b30 677 L.sub.a1-419 L.sub.b30 L.sub.b30 678 L.sub.a1-440 L.sub.b30 L.sub.b30 679 L.sub.a1-441 L.sub.b30 L.sub.b30 680 L.sub.a1-446 L.sub.b30 L.sub.b30 681 L.sub.a2-58 L.sub.b30 L.sub.b30 682 L.sub.a2-88 L.sub.b30 L.sub.b30 683 L.sub.a2-133 L.sub.b30 L.sub.b30 684 L.sub.a2-146 L.sub.b30 L.sub.b30 685 L.sub.a2-157 L.sub.b30 L.sub.b30 686 L.sub.a2-158 L.sub.b30 L.sub.b30 687 L.sub.a2-164 L.sub.b30 L.sub.b30 688 L.sub.a2-170 L.sub.b30 L.sub.b30 689 L.sub.a2-176 L.sub.b30 L.sub.b30 690 L.sub.a2-208 L.sub.b30 L.sub.b30 691 L.sub.a2-224 L.sub.b30 L.sub.b30 692 L.sub.a2-258 L.sub.b30 L.sub.b30 693 L.sub.a2-308 L.sub.b30 L.sub.b30 694 L.sub.a2-321 L.sub.b30 L.sub.b30 695 L.sub.a2-333 L.sub.b30 L.sub.b30 696 L.sub.a2-339 L.sub.b30 L.sub.b30 697 L.sub.a2-345 L.sub.b30 L.sub.b30 698 L.sub.a2-382 L.sub.b30 L.sub.b30 699 L.sub.a2-400 L.sub.b30 L.sub.b30 700 L.sub.a2-418 L.sub.b30 L.sub.b30 701 L.sub.a2-419 L.sub.b30 L.sub.b30 702 L.sub.a2-440 L.sub.b30 L.sub.b30 703 L.sub.a2-441 L.sub.b30 L.sub.b30 704 L.sub.a2-446 L.sub.b30 L.sub.b30 705 L.sub.a3-58 L.sub.b30 L.sub.b30 706 L.sub.a3-88 L.sub.b30 L.sub.b30 707 L.sub.a3-133 L.sub.b30 L.sub.b30 708 L.sub.a3-146 L.sub.b30 L.sub.b30 709 L.sub.a3-157 L.sub.b30 L.sub.b30 710 L.sub.a3-158 L.sub.b30 L.sub.b30 711 L.sub.a3-164 L.sub.b30 L.sub.b30 712 L.sub.a3-170 L.sub.b30 L.sub.b30 713 L.sub.a3-176 L.sub.b30 L.sub.b30 714 L.sub.a3-208 L.sub.b30 L.sub.b30 715 L.sub.a3-224 L.sub.b30 L.sub.b30 716 L.sub.a3-258 L.sub.b30 L.sub.b30 717 L.sub.a3-308 L.sub.b30 L.sub.b30 718 L.sub.a3-321 L.sub.b30 L.sub.b30 719 L.sub.a3-333 L.sub.b30 L.sub.b30 720 L.sub.a3-339 L.sub.b30 L.sub.b30 721 L.sub.a3-345 L.sub.b30 L.sub.b30 722 L.sub.a3-382 L.sub.b30 L.sub.b30 723 L.sub.a3-400 L.sub.b30 L.sub.b30 724 L.sub.a3-418 L.sub.b30 L.sub.b30 725 L.sub.a3-419 L.sub.b30 L.sub.b30 726 L.sub.a3-440 L.sub.b30 L.sub.b30 727 L.sub.a3-441 L.sub.b30 L.sub.b30 728 L.sub.a3-446 L.sub.b30 L.sub.b30 729 L.sub.a4-2 L.sub.b30 L.sub.b30 730 L.sub.a4-4 L.sub.b30 L.sub.b30 731 L.sub.a4-8 L.sub.b30 L.sub.b30 732 L.sub.a4-10 L.sub.b30 L.sub.b30 733 L.sub.a4-14 L.sub.b30 L.sub.b30 734 L.sub.a4-16 L.sub.b30 L.sub.b30 735 L.sub.a4-20 L.sub.b30 L.sub.b30 736 L.sub.a4-22 L.sub.b30 L.sub.b30 737 L.sub.a4-26 L.sub.b30 L.sub.b30 738 L.sub.a4-28 L.sub.b30 L.sub.b30 739 L.sub.a1-58 L.sub.b31 L.sub.b31 740 L.sub.a1-88 L.sub.b31 L.sub.b31 741 L.sub.a1-133 L.sub.b31 L.sub.b31 742 L.sub.a1-146 L.sub.b31 L.sub.b31 743 L.sub.a1-157 L.sub.b31 L.sub.b31 744 L.sub.a1-158 L.sub.b31 L.sub.b31 745 L.sub.a1-164 L.sub.b31 L.sub.b31 746 L.sub.a1-170 L.sub.b31 L.sub.b31 747 L.sub.a1-176 L.sub.b31 L.sub.b31 748 L.sub.a1-208 L.sub.b31 L.sub.b31 749 L.sub.a1-224 L.sub.b31 L.sub.b31 750 L.sub.a1-258 L.sub.b31 L.sub.b31 751 L.sub.a1-308 L.sub.b31 L.sub.b31 752 L.sub.a1-321 L.sub.b31 L.sub.b31 753 L.sub.a1-333 L.sub.b31 L.sub.b31 754 L.sub.a1-339 L.sub.b31 L.sub.b31 755 L.sub.a1-345 L.sub.b31 L.sub.b31 756 L.sub.a1-382 L.sub.b31 L.sub.b31 757 L.sub.a1-400 L.sub.b31 L.sub.b31 758 L.sub.a1-418 L.sub.b31 L.sub.b31 759 L.sub.a1-419 L.sub.b31 L.sub.b31 760 L.sub.a1-440 L.sub.b31 L.sub.b31 761 L.sub.a1-441 L.sub.b31 L.sub.b31 762 L.sub.a1-446 L.sub.b31 L.sub.b31 763 L.sub.a2-58 L.sub.b31 L.sub.b31 764 L.sub.a2-88 L.sub.b31 L.sub.b31 765 L.sub.a2-133 L.sub.b31 L.sub.b31 766 L.sub.a2-146 L.sub.b31 L.sub.b31 767 L.sub.a2-157 L.sub.b31 L.sub.b31 768 L.sub.a2-158 L.sub.b31 L.sub.b31 769 L.sub.a2-164 L.sub.b31 L.sub.b31 770 L.sub.a2-170 L.sub.b31 L.sub.b31 771 L.sub.a2-176 L.sub.b31 L.sub.b31 772 L.sub.a2-208 L.sub.b31 L.sub.b31 773 L.sub.a2-224 L.sub.b31 L.sub.b31 774 L.sub.a2-258 L.sub.b31 L.sub.b31 775 L.sub.a2-308 L.sub.b31 L.sub.b31 776 L.sub.a2-321 L.sub.b31 L.sub.b31 777 L.sub.a2-333 L.sub.b31 L.sub.b31 778 L.sub.a2-339 L.sub.b31 L.sub.b31 779 L.sub.a2-345 L.sub.b31 L.sub.b31 780 L.sub.a2-382 L.sub.b31 L.sub.b31 781 L.sub.a2-400 L.sub.b31 L.sub.b31 782 L.sub.a2-418 L.sub.b31 L.sub.b31 783 L.sub.a2-419 L.sub.b31 L.sub.b31 784 L.sub.a2-440 L.sub.b31 L.sub.b31 785 L.sub.a2-441 L.sub.b31 L.sub.b31 786 L.sub.a2-446 L.sub.b31 L.sub.b31 787 L.sub.a3-58 L.sub.b31 L.sub.b31 788 L.sub.a3-88 L.sub.b31 L.sub.b31 789 L.sub.a3-133 L.sub.b31 L.sub.b31 790 L.sub.a3-146 L.sub.b31 L.sub.b31 791 L.sub.a3-157 L.sub.b31 L.sub.b31 792 L.sub.a3-158 L.sub.b31 L.sub.b31 793 L.sub.a3-164 L.sub.b31 L.sub.b31 794 L.sub.a3-170 L.sub.b31 L.sub.b31 795 L.sub.a3-176 L.sub.b31 L.sub.b31 796 L.sub.a3-208 L.sub.b31 L.sub.b31 797 L.sub.a3-224 L.sub.b31 L.sub.b31 798 L.sub.a3-258 L.sub.b31 L.sub.b31 799 L.sub.a3-308 L.sub.b31 L.sub.b31 800 L.sub.a3-321 L.sub.b31 L.sub.b31 801 L.sub.a3-333 L.sub.b31 L.sub.b31 802 L.sub.a3-339 L.sub.b31 L.sub.b31 803 L.sub.a3-345 L.sub.b31 L.sub.b31 804 L.sub.a3-382 L.sub.b31 L.sub.b31 805 L.sub.a3-400 L.sub.b31 L.sub.b31 806 L.sub.a3-418 L.sub.b31 L.sub.b31 807 L.sub.a3-419 L.sub.b31 L.sub.b31 808 L.sub.a3-440 L.sub.b31 L.sub.b31 809 L.sub.a3-441 L.sub.b31 L.sub.b31 810 L.sub.a3-446 L.sub.b31 L.sub.b31 811 L.sub.a4-2 L.sub.b31 L.sub.b31 812 L.sub.a4-4 L.sub.b31 L.sub.b31 813 L.sub.a4-8 L.sub.b31 L.sub.b31 814 L.sub.a4-10 L.sub.b31 L.sub.b31 815 L.sub.a4-14 L.sub.b31 L.sub.b31 816 L.sub.a4-16 L.sub.b31 L.sub.b31 817 L.sub.a4-20 L.sub.b31 L.sub.b31 818 L.sub.a4-22 L.sub.b31 L.sub.b31 819 L.sub.a4-26 L.sub.b31 L.sub.b31 820 L.sub.a4-28 L.sub.b31 L.sub.b31 821 L.sub.a1-58 L.sub.b35 L.sub.b35 822 L.sub.a1-88 L.sub.b35 L.sub.b35 823 L.sub.a1-133 L.sub.b35 L.sub.b35 824 L.sub.a1-146 L.sub.b35 L.sub.b35 825 L.sub.a1-157 L.sub.b35 L.sub.b35 826 L.sub.a1-158 L.sub.b35 L.sub.b35 827 L.sub.a1-164 L.sub.b35 L.sub.b35 828 L.sub.a1-170 L.sub.b35 L.sub.b35 829 L.sub.a1-176 L.sub.b35 L.sub.b35 830 L.sub.a1-208 L.sub.b35 L.sub.b35 831 L.sub.a1-224 L.sub.b35 L.sub.b35 832 L.sub.a1-258 L.sub.b35 L.sub.b35 833 L.sub.a1-308 L.sub.b35 L.sub.b35 834 L.sub.a1-321 L.sub.b35 L.sub.b35 835 L.sub.a1-333 L.sub.b35 L.sub.b35 836 L.sub.a1-339 L.sub.b35 L.sub.b35 837 L.sub.a1-345 L.sub.b35 L.sub.b35 838 L.sub.a1-382 L.sub.b35 L.sub.b35 839 L.sub.a1-400 L.sub.b35 L.sub.b35 840 L.sub.a1-418 L.sub.b35 L.sub.b35 841 L.sub.a1-419 L.sub.b35 L.sub.b35 842 L.sub.a1-440 L.sub.b35 L.sub.b35 843 L.sub.a1-441 L.sub.b35 L.sub.b35 844 L.sub.a1-446 L.sub.b35 L.sub.b35 845 L.sub.a2-58 L.sub.b35 L.sub.b35 846 L.sub.a2-88 L.sub.b35 L.sub.b35 847 L.sub.a2-133 L.sub.b35 L.sub.b35 848 L.sub.a2-146 L.sub.b35 L.sub.b35 849 L.sub.a2-157 L.sub.b35 L.sub.b35 850 L.sub.a2-158 L.sub.b35 L.sub.b35 851 L.sub.a2-164 L.sub.b35 L.sub.b35 852 L.sub.a2-170 L.sub.b35 L.sub.b35 853 L.sub.a2-176 L.sub.b35 L.sub.b35 854 L.sub.a2-208 L.sub.b35 L.sub.b35 855 L.sub.a2-224 L.sub.b35 L.sub.b35 856 L.sub.a2-258 L.sub.b35 L.sub.b35 857 L.sub.a2-308 L.sub.b35 L.sub.b35 858 L.sub.a2-321 L.sub.b35 L.sub.b35 859 L.sub.a2-333 L.sub.b35 L.sub.b35 860 L.sub.a2-339 L.sub.b35 L.sub.b35 861 L.sub.a2-345 L.sub.b35 L.sub.b35 862 L.sub.a2-382 L.sub.b35 L.sub.b35 863 L.sub.a2-400 L.sub.b35 L.sub.b35 864 L.sub.a2-418 L.sub.b35 L.sub.b35 865 L.sub.a2-419 L.sub.b35 L.sub.b35 866 L.sub.a2-440 L.sub.b35 L.sub.b35 867 L.sub.a2-441 L.sub.b35 L.sub.b35 868 L.sub.a2-446 L.sub.b35 L.sub.b35 869 L.sub.a3-58 L.sub.b35 L.sub.b35 870 L.sub.a3-88 L.sub.b35 L.sub.b35 871 L.sub.a3-133 L.sub.b35 L.sub.b35 872 L.sub.a3-146 L.sub.b35 L.sub.b35 873 L.sub.a3-157 L.sub.b35 L.sub.b35 874 L.sub.a3-158 L.sub.b35 L.sub.b35 875 L.sub.a3-164 L.sub.b35 L.sub.b35 876 L.sub.a3-170 L.sub.b35 L.sub.b35 877 L.sub.a3-176 L.sub.b35 L.sub.b35 878 L.sub.a3-208 L.sub.b35 L.sub.b35 879 L.sub.a3-224 L.sub.b35 L.sub.b35 880 L.sub.a3-258 L.sub.b35 L.sub.b35 881 L.sub.a3-308 L.sub.b35 L.sub.b35 882 L.sub.a3-321 L.sub.b35 L.sub.b35 883 L.sub.a3-333 L.sub.b35 L.sub.b35 884 L.sub.a3-339 L.sub.b35 L.sub.b35 885 L.sub.a3-345 L.sub.b35 L.sub.b35 886 L.sub.a3-382 L.sub.b35 L.sub.b35 887 L.sub.a3-400 L.sub.b35 L.sub.b35 888 L.sub.a3-418 L.sub.b35 L.sub.b35 889 L.sub.a3-419 L.sub.b35 L.sub.b35 890 L.sub.a3-440 L.sub.b35 L.sub.b35 891 L.sub.a3-441 L.sub.b35 L.sub.b35 892 L.sub.a3-446 L.sub.b35 L.sub.b35 893 L.sub.a4-2 L.sub.b35 L.sub.b35 894 L.sub.a4-4 L.sub.b35 L.sub.b35 895 L.sub.a4-8 L.sub.b35 L.sub.b35 896 L.sub.a4-10 L.sub.b35 L.sub.b35 897 L.sub.a4-14 L.sub.b35 L.sub.b35 898 L.sub.a4-16 L.sub.b35 L.sub.b35 899 L.sub.a4-20 L.sub.b35 L.sub.b35 900 L.sub.a4-22 L.sub.b35 L.sub.b35 901 L.sub.a4-26 L.sub.b35 L.sub.b35 902 L.sub.a4-28 L.sub.b35 L.sub.b35 903 L.sub.a1-58 L.sub.b37 L.sub.b37 904 L.sub.a1-88 L.sub.b37 L.sub.b37 905 L.sub.a1-133 L.sub.b37 L.sub.b37 906 L.sub.a1-146 L.sub.b37 L.sub.b37 907 L.sub.a1-157 L.sub.b37 L.sub.b37 908 L.sub.a1-158 L.sub.b37 L.sub.b37 909 L.sub.a1-164 L.sub.b37 L.sub.b37 910 L.sub.a1-170 L.sub.b37 L.sub.b37 911 L.sub.a1-176 L.sub.b37 L.sub.b37 912 L.sub.a1-208 L.sub.b37 L.sub.b37 913 L.sub.a1-224 L.sub.b37 L.sub.b37 914 L.sub.a1-258 L.sub.b37 L.sub.b37 915 L.sub.a1-308 L.sub.b37 L.sub.b37 916 L.sub.a1-321 L.sub.b37 L.sub.b37 917 L.sub.a1-333 L.sub.b37 L.sub.b37 918 L.sub.a1-339 L.sub.b37 L.sub.b37 919 L.sub.a1-345 L.sub.b37 L.sub.b37 920 L.sub.a1-382 L.sub.b37 L.sub.b37 921 L.sub.a1-400 L.sub.b37 L.sub.b37 922 L.sub.a1-418 L.sub.b37 L.sub.b37 923 L.sub.a1-419 L.sub.b37 L.sub.b37 924 L.sub.a1-440 L.sub.b37 L.sub.b37 925 L.sub.a1-441 L.sub.b37 L.sub.b37 926 L.sub.a1-446 L.sub.b37 L.sub.b37 927 L.sub.a2-58 L.sub.b37 L.sub.b37 928 L.sub.a2-88 L.sub.b37 L.sub.b37 929 L.sub.a2-133 L.sub.b37 L.sub.b37 930 L.sub.a2-146 L.sub.b37 L.sub.b37 931 L.sub.a2-157 L.sub.b37 L.sub.b37 932 L.sub.a2-158 L.sub.b37 L.sub.b37 933 L.sub.a2-164 L.sub.b37 L.sub.b37 934 L.sub.a2-170 L.sub.b37 L.sub.b37 935 L.sub.a2-176 L.sub.b37 L.sub.b37 936 L.sub.a2-208 L.sub.b37 L.sub.b37 937 L.sub.a2-224 L.sub.b37 L.sub.b37 938 L.sub.a2-258 L.sub.b37 L.sub.b37 939 L.sub.a2-308 L.sub.b37 L.sub.b37 940 L.sub.a2-321 L.sub.b37 L.sub.b37 941 L.sub.a2-333 L.sub.b37 L.sub.b37 942 L.sub.a2-339 L.sub.b37 L.sub.b37 943 L.sub.a2-345 L.sub.b37 L.sub.b37 944 L.sub.a2-382 L.sub.b37 L.sub.b37 945 L.sub.a2-400 L.sub.b37 L.sub.b37 946 L.sub.a2-418 L.sub.b37 L.sub.b37 947 L.sub.a2-419 L.sub.b37 L.sub.b37 948 L.sub.a2-440 L.sub.b37 L.sub.b37 949 L.sub.a2-441 L.sub.b37 L.sub.b37 950 L.sub.a2-446 L.sub.b37 L.sub.b37 951 L.sub.a3-58 L.sub.b37 L.sub.b37 952 L.sub.a3-88 L.sub.b37 L.sub.b37 953 L.sub.a3-133 L.sub.b37 L.sub.b37 954 L.sub.a3-146 L.sub.b37 L.sub.b37 955 L.sub.a3-157 L.sub.b37 L.sub.b37 956 L.sub.a3-158 L.sub.b37 L.sub.b37 957 L.sub.a3-164 L.sub.b37 L.sub.b37 958 L.sub.a3-170 L.sub.b37 L.sub.b37 959 L.sub.a3-176 L.sub.b37 L.sub.b37 960 L.sub.a3-208 L.sub.b37 L.sub.b37 961 L.sub.a3-224 L.sub.b37 L.sub.b37 962 L.sub.a3-258 L.sub.b37 L.sub.b37 963 L.sub.a3-308 L.sub.b37 L.sub.b37 964 L.sub.a3-321 L.sub.b37 L.sub.b37 965 L.sub.a3-333 L.sub.b37 L.sub.b37 966 L.sub.a3-339 L.sub.b37 L.sub.b37 967 L.sub.a3-345 L.sub.b37 L.sub.b37 968 L.sub.a3-382 L.sub.b37 L.sub.b37 969 L.sub.a3-400 L.sub.b37 L.sub.b37 970 L.sub.a3-418 L.sub.b37 L.sub.b37 971 L.sub.a3-419 L.sub.b37 L.sub.b37 972 L.sub.a3-440 L.sub.b37 L.sub.b37 973 L.sub.a3-441 L.sub.b37 L.sub.b37 974 L.sub.a3-446 L.sub.b37 L.sub.b37 975 L.sub.a4-2 L.sub.b37 L.sub.b37 976 L.sub.a4-4 L.sub.b37 L.sub.b37 977 L.sub.a4-8 L.sub.b37 L.sub.b37 978 L.sub.a4-10 L.sub.b37 L.sub.b37 979 L.sub.a4-14 L.sub.b37 L.sub.b37 980 L.sub.a4-16 L.sub.b37 L.sub.b37 981 L.sub.a4-20 L.sub.b37 L.sub.b37 982 L.sub.a4-22 L.sub.b37 L.sub.b37 983 L.sub.a4-26 L.sub.b37 L.sub.b37 984 L.sub.a4-28 L.sub.b37 L.sub.b37 985 L.sub.a1-58 L.sub.b38 L.sub.b38 986 L.sub.a1-88 L.sub.b38 L.sub.b38 987 L.sub.a1-133 L.sub.b38 L.sub.b38 988 L.sub.a1-146 L.sub.b38 L.sub.b38 989 L.sub.a1-157 L.sub.b38 L.sub.b38 990 L.sub.a1-158 L.sub.b38 L.sub.b38 991 L.sub.a1-164 L.sub.b38 L.sub.b38 992 L.sub.a1-170 L.sub.b38 L.sub.b38 993 L.sub.a1-176 L.sub.b38 L.sub.b38 994 L.sub.a1-208 L.sub.b38 L.sub.b38 995 L.sub.a1-224 L.sub.b38 L.sub.b38 996 L.sub.a1-258 L.sub.b38 L.sub.b38 997 L.sub.a1-308 L.sub.b38 L.sub.b38 998 L.sub.a1-321 L.sub.b38 L.sub.b38 999 L.sub.a1-333 L.sub.b38 L.sub.b38 1000 L.sub.a1-339 L.sub.b38 L.sub.b38 1001 L.sub.a1-345 L.sub.b38 L.sub.b38 1002 L.sub.a1-382 L.sub.b38 L.sub.b38 1003 L.sub.a1-400 L.sub.b38 L.sub.b38 1004 L.sub.a1-418 L.sub.b38 L.sub.b38 1005 L.sub.a1-419 L.sub.b38 L.sub.b38 1006 L.sub.a1-440 L.sub.b38 L.sub.b38 1007 L.sub.a1-441 L.sub.b38 L.sub.b38 1008 L.sub.a1-446 L.sub.b38 L.sub.b38 1009 L.sub.a2-58 L.sub.b38 L.sub.b38 1010 L.sub.a2-88 L.sub.b38 L.sub.b38 1011 L.sub.a2-133 L.sub.b38 L.sub.b38 1012 L.sub.a2-146 L.sub.b38 L.sub.b38 1013 L.sub.a2-157 L.sub.b38 L.sub.b38 1014 L.sub.a2-158 L.sub.b38 L.sub.b38 1015 L.sub.a2-164 L.sub.b38 L.sub.b38 1016 L.sub.a2-170 L.sub.b38 L.sub.b38 1017 L.sub.a2-176 L.sub.b38 L.sub.b38 1018 L.sub.a2-208 L.sub.b38 L.sub.b38 1019 L.sub.a2-224 L.sub.b38 L.sub.b38 1020 L.sub.a2-258 L.sub.b38 L.sub.b38 1021 L.sub.a2-308 L.sub.b38 L.sub.b38 1022 L.sub.a2-321 L.sub.b38 L.sub.b38 1023 L.sub.a2-333 L.sub.b38 L.sub.b38 1024 L.sub.a2-339 L.sub.b38 L.sub.b38 1025 L.sub.a2-345 L.sub.b38 L.sub.b38 1026 L.sub.a2-382 L.sub.b38 L.sub.b38 1027 L.sub.a2-400 L.sub.b38 L.sub.b38 1028 L.sub.a2-418 L.sub.b38 L.sub.b38 1029 L.sub.a2-419 L.sub.b38 L.sub.b38 1030 L.sub.a2-440 L.sub.b38 L.sub.b38 1031 L.sub.a2-441 L.sub.b38 L.sub.b38 1032 L.sub.a2-446 L.sub.b38 L.sub.b38 1033 L.sub.a3-58 L.sub.b38 L.sub.b38 1034 L.sub.a3-88 L.sub.b38 L.sub.b38 1035 L.sub.a3-133 L.sub.b38 L.sub.b38 1036 L.sub.a3-146 L.sub.b38 L.sub.b38 1037 L.sub.a3-157 L.sub.b38 L.sub.b38 1038 L.sub.a3-158 L.sub.b38 L.sub.b38 1039 L.sub.a3-164 L.sub.b38 L.sub.b38 1040 L.sub.a3-170 L.sub.b38 L.sub.b38 1041 L.sub.a3-176 L.sub.b38 L.sub.b38 1042 L.sub.a3-208 L.sub.b38 L.sub.b38 1043 L.sub.a3-224 L.sub.b38 L.sub.b38 1044 L.sub.a3-258 L.sub.b38 L.sub.b38 1045 L.sub.a3-308 L.sub.b38 L.sub.b38 1046 L.sub.a3-321 L.sub.b38 L.sub.b38 1047 L.sub.a3-333 L.sub.b38 L.sub.b38 1048 L.sub.a3-339 L.sub.b38 L.sub.b38 1049 L.sub.a3-345 L.sub.b38 L.sub.b38 1050 L.sub.a3-382 L.sub.b38 L.sub.b38 1051 L.sub.a3-400 L.sub.b38 L.sub.b38 1052 L.sub.a3-418 L.sub.b38 L.sub.b38 1053 L.sub.a3-419 L.sub.b38 L.sub.b38 1054 L.sub.a3-440 L.sub.b38 L.sub.b38 1055 L.sub.a3-441 L.sub.b38 L.sub.b38 1056 L.sub.a3-446 L.sub.b38 L.sub.b38 1057 L.sub.a4-2 L.sub.b38 L.sub.b38 1058 L.sub.a4-4 L.sub.b38 L.sub.b38 1059 L.sub.a4-8 L.sub.b38 L.sub.b38 1060 L.sub.a4-10 L.sub.b38 L.sub.b38 1061 L.sub.a4-14 L.sub.b38 L.sub.b38 1062 L.sub.a4-16 L.sub.b38 L.sub.b38 1063 L.sub.a4-20 L.sub.b38 L.sub.b38 1064 L.sub.a4-22 L.sub.b38 L.sub.b38 1065 L.sub.a4-26 L.sub.b38 L.sub.b38 1066 L.sub.a4-28 L.sub.b38 L.sub.b38 1067 L.sub.a1-58 L.sub.b40 L.sub.b40 1068 L.sub.a1-88 L.sub.b40 L.sub.b40 1069 L.sub.a1-133 L.sub.b40 L.sub.b40 1070 L.sub.a1-146 L.sub.b40 L.sub.b40 1071 L.sub.a1-157 L.sub.b40 L.sub.b40 1072 L.sub.a1-158 L.sub.b40 L.sub.b40 1073 L.sub.a1-164 L.sub.b40 L.sub.b40 1074 L.sub.a1-170 L.sub.b40 L.sub.b40 1075 L.sub.a1-176 L.sub.b40 L.sub.b40 1076 L.sub.a1-208 L.sub.b40 L.sub.b40 1077 L.sub.a1-224 L.sub.b40 L.sub.b40 1078 L.sub.a1-258 L.sub.b40 L.sub.b40 1079 L.sub.a1-308 L.sub.b40 L.sub.b40 1080 L.sub.a1-321 L.sub.b40 L.sub.b40 1081 L.sub.a1-333 L.sub.b40 L.sub.b40 1082 L.sub.a1-339 L.sub.b40 L.sub.b40 1083 L.sub.a1-345 L.sub.b40 L.sub.b40 1084 L.sub.a1-382 L.sub.b40 L.sub.b40 1085 L.sub.a1-400 L.sub.b40 L.sub.b40 1086 L.sub.a1-418 L.sub.b40 L.sub.b40 1087 L.sub.a1-419 L.sub.b40 L.sub.b40 1088 L.sub.a1-440 L.sub.b40 L.sub.b40 1089 L.sub.a1-441 L.sub.b40 L.sub.b40 1090 L.sub.a1-446 L.sub.b40 L.sub.b40 1091 L.sub.a2-58 L.sub.b40 L.sub.b40 1092 L.sub.a2-88 L.sub.b40 L.sub.b40 1093 L.sub.a2-133 L.sub.b40 L.sub.b40 1094 L.sub.a2-146 L.sub.b40 L.sub.b40 1095 L.sub.a2-157 L.sub.b40 L.sub.b40 1096 L.sub.a2-158 L.sub.b40 L.sub.b40 1097 L.sub.a2-164 L.sub.b40 L.sub.b40 1098 L.sub.a2-170 L.sub.b40 L.sub.b40 1099 L.sub.a2-176 L.sub.b40 L.sub.b40 1100 L.sub.a2-208 L.sub.b40 L.sub.b40 1101 L.sub.a2-224 L.sub.b40 L.sub.b40 1102 L.sub.a2-258 L.sub.b40 L.sub.b40 1103 L.sub.a2-308 L.sub.b40 L.sub.b40 1104 L.sub.a2-321 L.sub.b40 L.sub.b40 1105 L.sub.a2-333 L.sub.b40 L.sub.b40 1106 L.sub.a2-339 L.sub.b40 L.sub.b40 1107 L.sub.a2-345 L.sub.b40 L.sub.b40 1108 L.sub.a2-382 L.sub.b40 L.sub.b40 1109 L.sub.a2-400 L.sub.b40 L.sub.b40 1110 L.sub.a2-418 L.sub.b40 L.sub.b40 1111 L.sub.a2-419 L.sub.b40 L.sub.b40 1112 L.sub.a2-440 L.sub.b40 L.sub.b40 1113 L.sub.a2-441 L.sub.b40 L.sub.b40 1114 L.sub.a2-446 L.sub.b40 L.sub.b40 1115 L.sub.a3-58 L.sub.b40 L.sub.b40 1116 L.sub.a3-88 L.sub.b40 L.sub.b40 1117 L.sub.a3-133 L.sub.b40 L.sub.b40 1118 L.sub.a3-146 L.sub.b40 L.sub.b40 1119 L.sub.a3-157 L.sub.b40 L.sub.b40 1120 L.sub.a3-158 L.sub.b40 L.sub.b40 1121 L.sub.a3-164 L.sub.b40 L.sub.b40 1122 L.sub.a3-170 L.sub.b40 L.sub.b40 1123 L.sub.a3-176 L.sub.b40 L.sub.b40 1124 L.sub.a3-208 L.sub.b40 L.sub.b40 1125 L.sub.a3-224 L.sub.b40 L.sub.b40 1126 L.sub.a3-258 L.sub.b40 L.sub.b40 1127 L.sub.a3-308 L.sub.b40 L.sub.b40 1128 L.sub.a3-321 L.sub.b40 L.sub.b40 1129 L.sub.a3-333 L.sub.b40 L.sub.b40 1130 L.sub.a3-339 L.sub.b40 L.sub.b40 1131 L.sub.a3-345 L.sub.b40 L.sub.b40 1132 L.sub.a3-382 L.sub.b40 L.sub.b40 1133 L.sub.a3-400 L.sub.b40 L.sub.b40 1134 L.sub.a3-418 L.sub.b40 L.sub.b40 1135 L.sub.a3-419 L.sub.b40 L.sub.b40 1136 L.sub.a3-440 L.sub.b40 L.sub.b40 1137 L.sub.a3-441 L.sub.b40 L.sub.b40 1138 L.sub.a3-446 L.sub.b40 L.sub.b40 1139 L.sub.a4-2 L.sub.b40 L.sub.b40 1140 L.sub.a4-4 L.sub.b40 L.sub.b40 1141 L.sub.a4-8 L.sub.b40 L.sub.b40 1142 L.sub.a4-10 L.sub.b40 L.sub.b40 1143 L.sub.a4-14 L.sub.b40 L.sub.b40 1144 L.sub.a4-16 L.sub.b40 L.sub.b40 1145 L.sub.a4-20 L.sub.b40 L.sub.b40 1146 L.sub.a4-22 L.sub.b40 L.sub.b40 1147 L.sub.a4-26 L.sub.b40 L.sub.b40 1148 L.sub.a4-28 L.sub.b40 L.sub.b40 1149 L.sub.a1-58 L.sub.b71 L.sub.b71 1150 L.sub.a1-88 L.sub.b71 L.sub.b71 1151 L.sub.a1-133 L.sub.b71 L.sub.b71 1152 L.sub.a1-146 L.sub.b71 L.sub.b71 1153 L.sub.a1-157 L.sub.b71 L.sub.b71 1154 L.sub.a1-158 L.sub.b71 L.sub.b71 1155 L.sub.a1-164 L.sub.b71 L.sub.b71 1156 L.sub.a1-170 L.sub.b71 L.sub.b71 1157 L.sub.a1-176 L.sub.b71 L.sub.b71 1158 L.sub.a1-208 L.sub.b71 L.sub.b71 1159 L.sub.a1-224 L.sub.b71 L.sub.b71 1160 L.sub.a1-258 L.sub.b71 L.sub.b71 1161 L.sub.a1-308 L.sub.b71 L.sub.b71 1162 L.sub.a1-321 L.sub.b71 L.sub.b71 1163 L.sub.a1-333 L.sub.b71 L.sub.b71 1164 L.sub.a1-339 L.sub.b71 L.sub.b71 1165 L.sub.a1-345 L.sub.b71 L.sub.b71 1166 L.sub.a1-382 L.sub.b71 L.sub.b71 1167 L.sub.a1-400 L.sub.b71 L.sub.b71 1168 L.sub.a1-418 L.sub.b71 L.sub.b71 1169 L.sub.a1-419 L.sub.b71 L.sub.b71 1170 L.sub.a1-440 L.sub.b71 L.sub.b71 1171 L.sub.a1-441 L.sub.b71 L.sub.b71 1172 L.sub.a1-446 L.sub.b71 L.sub.b71 1173 L.sub.a2-58 L.sub.b71 L.sub.b71 1174 L.sub.a2-88 L.sub.b71 L.sub.b71 1175 L.sub.a2-133 L.sub.b71 L.sub.b71 1176 L.sub.a2-146 L.sub.b71 L.sub.b71 1177 L.sub.a2-157 L.sub.b71 L.sub.b71 1178 L.sub.a2-158 L.sub.b71 L.sub.b71 1179 L.sub.a2-164 L.sub.b71 L.sub.b71 1180 L.sub.a2-170 L.sub.b71 L.sub.b71 1181 L.sub.a2-176 L.sub.b71 L.sub.b71 1182 L.sub.a2-208 L.sub.b71 L.sub.b71 1183 L.sub.a2-224 L.sub.b71 L.sub.b71 1184 L.sub.a2-258 L.sub.b71 L.sub.b71 1185 L.sub.a2-308 L.sub.b71 L.sub.b71 1186 L.sub.a2-321 L.sub.b71 L.sub.b71 1187 L.sub.a2-333 L.sub.b71 L.sub.b71 1188 L.sub.a2-339 L.sub.b71 L.sub.b71 1189 L.sub.a2-345 L.sub.b71 L.sub.b71 1190 L.sub.a2-382 L.sub.b71 L.sub.b71 1191 L.sub.a2-400 L.sub.b71 L.sub.b71 1192 L.sub.a2-418 L.sub.b71 L.sub.b71 1193 L.sub.a2-419 L.sub.b71 L.sub.b71 1194 L.sub.a2-440 L.sub.b71 L.sub.b71 1195 L.sub.a2-441 L.sub.b71 L.sub.b71 1196 L.sub.a2-446 L.sub.b71 L.sub.b71 1197 L.sub.a3-58 L.sub.b71 L.sub.b71 1198 L.sub.a3-88 L.sub.b71 L.sub.b71 1199 L.sub.a3-133 L.sub.b71 L.sub.b71 1200 L.sub.a3-146 L.sub.b71 L.sub.b71 1201 L.sub.a3-157 L.sub.b71 L.sub.b71 1202 L.sub.a3-158 L.sub.b71 L.sub.b71 1203 L.sub.a3-164 L.sub.b71 L.sub.b71 1204 L.sub.a3-170 L.sub.b71 L.sub.b71 1205 L.sub.a3-176 L.sub.b71 L.sub.b71 1206 L.sub.a3-208 L.sub.b71 L.sub.b71 1207 L.sub.a3-224 L.sub.b71 L.sub.b71 1208 L.sub.a3-258 L.sub.b71 L.sub.b71 1209 L.sub.a3-308 L.sub.b71 L.sub.b71 1210 L.sub.a3-321 L.sub.b71 L.sub.b71 1211 L.sub.a3-333 L.sub.b71 L.sub.b71 1212 L.sub.a3-339 L.sub.b71 L.sub.b71 1213 L.sub.a3-345 L.sub.b71 L.sub.b71 1214 L.sub.a3-382 L.sub.b71 L.sub.b71 1215 L.sub.a3-400 L.sub.b71 L.sub.b71 1216 L.sub.a3-418 L.sub.b71 L.sub.b71 1217 L.sub.a3-419 L.sub.b71 L.sub.b71 1218 L.sub.a3-440 L.sub.b71 L.sub.b71 1219 L.sub.a3-441 L.sub.b71 L.sub.b71 1220 L.sub.a3-446 L.sub.b71 L.sub.b71 1221 L.sub.a4-2 L.sub.b71 L.sub.b71 1222 L.sub.a4-4 L.sub.b71 L.sub.b71 1223 L.sub.a4-8 L.sub.b71 L.sub.b71 1224 L.sub.a4-10 L.sub.b71 L.sub.b71 1225 L.sub.a4-14 L.sub.b71 L.sub.b71 1226 L.sub.a4-16 L.sub.b71 L.sub.b71 1227 L.sub.a4-20 L.sub.b71 L.sub.b71 1228 L.sub.a4-22 L.sub.b71 L.sub.b71 1229 L.sub.a4-26 L.sub.b71 L.sub.b71 1230 L.sub.a4-28 L.sub.b71 L.sub.b71 1231 L.sub.a1-58 L.sub.b72 L.sub.b72 1232 L.sub.a1-88 L.sub.b72 L.sub.b72 1233 L.sub.a1-133 L.sub.b72 L.sub.b72 1234 L.sub.a1-146 L.sub.b72 L.sub.b72 1235 L.sub.a1-157 L.sub.b72 L.sub.b72 1236 L.sub.a1-158 L.sub.b72 L.sub.b72 1237 L.sub.a1-164 L.sub.b72 L.sub.b72 1238 L.sub.a1-170 L.sub.b72 L.sub.b72 1239 L.sub.a1-176 L.sub.b72 L.sub.b72 1240 L.sub.a1-208 L.sub.b72 L.sub.b72 1241 L.sub.a1-224 L.sub.b72 L.sub.b72 1242 L.sub.a1-258 L.sub.b72 L.sub.b72 1243 L.sub.a1-308 L.sub.b72 L.sub.b72 1244 L.sub.a1-321 L.sub.b72 L.sub.b72 1245 L.sub.a1-333 L.sub.b72 L.sub.b72 1246 L.sub.a1-339 L.sub.b72 L.sub.b72 1247 L.sub.a1-345 L.sub.b72 L.sub.b72 1248 L.sub.a1-382 L.sub.b72 L.sub.b72 1249 L.sub.a1-400 L.sub.b72 L.sub.b72 1250 L.sub.a1-418 L.sub.b72 L.sub.b72 1251 L.sub.a1-419 L.sub.b72 L.sub.b72 1252 L.sub.a1-440 L.sub.b72 L.sub.b72 1253 L.sub.a1-441 L.sub.b72 L.sub.b72 1254 L.sub.a1-446 L.sub.b72 L.sub.b72 1255 L.sub.a2-58 L.sub.b72 L.sub.b72 1256 L.sub.a2-88 L.sub.b72 L.sub.b72 1257 L.sub.a2-133 L.sub.b72 L.sub.b72 1258 L.sub.a2-146 L.sub.b72 L.sub.b72 1259 L.sub.a2-157 L.sub.b72 L.sub.b72 1260 L.sub.a2-158 L.sub.b72 L.sub.b72 1261 L.sub.a2-164 L.sub.b72 L.sub.b72 1262 L.sub.a2-170 L.sub.b72 L.sub.b72 1263 L.sub.a2-176 L.sub.b72 L.sub.b72 1264 L.sub.a2-208 L.sub.b72 L.sub.b72 1265 L.sub.a2-224 L.sub.b72 L.sub.b72 1266 L.sub.a2-258 L.sub.b72 L.sub.b72 1267 L.sub.a2-308 L.sub.b72 L.sub.b72 1268 L.sub.a2-321 L.sub.b72 L.sub.b72 1269 L.sub.a2-333 L.sub.b72 L.sub.b72 1270 L.sub.a2-339 L.sub.b72 L.sub.b72 1271 L.sub.a2-345 L.sub.b72 L.sub.b72 1272 L.sub.a2-382 L.sub.b72 L.sub.b72 1273 L.sub.a2-400 L.sub.b72 L.sub.b72 1274 L.sub.a2-418 L.sub.b72 L.sub.b72 1275 L.sub.a2-419 L.sub.b72 L.sub.b72 1276 L.sub.a2-440 L.sub.b72 L.sub.b72 1277 L.sub.a2-441 L.sub.b72 L.sub.b72 1278 L.sub.a2-446 L.sub.b72 L.sub.b72 1279 L.sub.a3-58 L.sub.b72 L.sub.b72 1280 L.sub.a3-88 L.sub.b72 L.sub.b72 1281 L.sub.a3-133 L.sub.b72 L.sub.b72 1282 L.sub.a3-146 L.sub.b72 L.sub.b72 1283 L.sub.a3-157 L.sub.b72 L.sub.b72 1284 L.sub.a3-158 L.sub.b72 L.sub.b72 1285 L.sub.a3-164 L.sub.b72 L.sub.b72 1286 L.sub.a3-170 L.sub.b72 L.sub.b72 1287 L.sub.a3-176 L.sub.b72 L.sub.b72 1288 L.sub.a3-208 L.sub.b72 L.sub.b72 1289 L.sub.a3-224 L.sub.b72 L.sub.b72 1290 L.sub.a3-258 L.sub.b72 L.sub.b72 1291 L.sub.a3-308 L.sub.b72 L.sub.b72 1292 L.sub.a3-321 L.sub.b72 L.sub.b72 1293 L.sub.a3-333 L.sub.b72 L.sub.b72 1294 L.sub.a3-339 L.sub.b72 L.sub.b72 1295 L.sub.a3-345 L.sub.b72 L.sub.b72 1296 L.sub.a3-382 L.sub.b72 L.sub.b72 1297 L.sub.a3-400 L.sub.b72 L.sub.b72 1298 L.sub.a3-418 L.sub.b72 L.sub.b72 1299 L.sub.a3-419 L.sub.b72 L.sub.b72 1300 L.sub.a3-440 L.sub.b72 L.sub.b72 1301 L.sub.a3-441 L.sub.b72 L.sub.b72 1302 L.sub.a3-446 L.sub.b72 L.sub.b72 1303 L.sub.a4-2 L.sub.b72 L.sub.b72 1304 L.sub.a4-4 L.sub.b72 L.sub.b72 1305 L.sub.a4-8 L.sub.b72 L.sub.b72 1306 L.sub.a4-10 L.sub.b72 L.sub.b72 1307 L.sub.a4-14 L.sub.b72 L.sub.b72 1308 L.sub.a4-16 L.sub.b72 L.sub.b72 1309 L.sub.a4-20 L.sub.b72 L.sub.b72 1310 L.sub.a4-22 L.sub.b72 L.sub.b72 1311 L.sub.a4-26 L.sub.b72 L.sub.b72 1312 L.sub.a4-28 L.sub.b72 L.sub.b72 1313 L.sub.a1-58 L.sub.b79 L.sub.b79 1314 L.sub.a1-88 L.sub.b79 L.sub.b79 1315 L.sub.a1-133 L.sub.b79 L.sub.b79 1316 L.sub.a1-146 L.sub.b79 L.sub.b79 1317 L.sub.a1-157 L.sub.b79 L.sub.b79 1318 L.sub.a1-158 L.sub.b79 L.sub.b79 1319 L.sub.a1-164 L.sub.b79 L.sub.b79 1320 L.sub.a1-170 L.sub.b79 L.sub.b79 1321 L.sub.a1-176 L.sub.b79 L.sub.b79 1322 L.sub.a1-208 L.sub.b79 L.sub.b79 1323 L.sub.a1-224 L.sub.b79 L.sub.b79 1324 L.sub.a1-258 L.sub.b79 L.sub.b79 1325 L.sub.a1-308 L.sub.b79 L.sub.b79 1326 L.sub.a1-321 L.sub.b79 L.sub.b79 1327 L.sub.a1-333 L.sub.b79 L.sub.b79 1328 L.sub.a1-339 L.sub.b79 L.sub.b79 1329 L.sub.a1-345 L.sub.b79 L.sub.b79 1330 L.sub.a1-382 L.sub.b79 L.sub.b79 1331 L.sub.a1-400 L.sub.b79 L.sub.b79 1332 L.sub.a1-418 L.sub.b79 L.sub.b79 1333 L.sub.a1-419 L.sub.b79 L.sub.b79 1334 L.sub.a1-440 L.sub.b79 L.sub.b79 1335 L.sub.a1-441 L.sub.b79 L.sub.b79 1336 L.sub.a1-446 L.sub.b79 L.sub.b79 1337 L.sub.a2-58 L.sub.b79 L.sub.b79 1338 L.sub.a2-88 L.sub.b79 L.sub.b79 1339 L.sub.a2-133 L.sub.b79 L.sub.b79 1340 L.sub.a2-146 L.sub.b79 L.sub.b79 1341 L.sub.a2-157 L.sub.b79 L.sub.b79 1342 L.sub.a2-158 L.sub.b79 L.sub.b79 1343 L.sub.a2-164 L.sub.b79 L.sub.b79 1344 L.sub.a2-170 L.sub.b79 L.sub.b79 1345 L.sub.a2-176 L.sub.b79 L.sub.b79 1346 L.sub.a2-208 L.sub.b79 L.sub.b79 1347 L.sub.a2-224 L.sub.b79 L.sub.b79 1348 L.sub.a2-258 L.sub.b79 L.sub.b79 1349 L.sub.a2-308 L.sub.b79 L.sub.b79 1350 L.sub.a2-321 L.sub.b79 L.sub.b79 1351 L.sub.a2-333 L.sub.b79 L.sub.b79 1352 L.sub.a2-339 L.sub.b79 L.sub.b79 1353 L.sub.a2-345 L.sub.b79 L.sub.b79 1354 L.sub.a2-382 L.sub.b79 L.sub.b79 1355 L.sub.a2-400 L.sub.b79 L.sub.b79 1356 L.sub.a2-418 L.sub.b79 L.sub.b79 1357 L.sub.a2-419 L.sub.b79 L.sub.b79 1358 L.sub.a2-440 L.sub.b79 L.sub.b79 1359 L.sub.a2-441 L.sub.b79 L.sub.b79 1360 L.sub.a2-446 L.sub.b79 L.sub.b79 1361 L.sub.a3-58 L.sub.b79 L.sub.b79 1362 L.sub.a3-88 L.sub.b79 L.sub.b79 1363 L.sub.a3-133 L.sub.b79 L.sub.b79 1364 L.sub.a3-146 L.sub.b79 L.sub.b79 1365 L.sub.a3-157 L.sub.b79 L.sub.b79 1366 L.sub.a3-158 L.sub.b79 L.sub.b79 1367 L.sub.a3-164 L.sub.b79 L.sub.b79 1368 L.sub.a3-170 L.sub.b79 L.sub.b79 1369 L.sub.a3-176 L.sub.b79 L.sub.b79 1370 L.sub.a3-208 L.sub.b79 L.sub.b79 1371 L.sub.a3-224 L.sub.b79 L.sub.b79 1372 L.sub.a3-258 L.sub.b79 L.sub.b79 1373 L.sub.a3-308 L.sub.b79 L.sub.b79 1374 L.sub.a3-321 L.sub.b79 L.sub.b79 1375 L.sub.a3-333 L.sub.b79 L.sub.b79 1376 L.sub.a3-339 L.sub.b79 L.sub.b79 1377 L.sub.a3-345 L.sub.b79 L.sub.b79 1378 L.sub.a3-382 L.sub.b79 L.sub.b79 1379 L.sub.a3-400 L.sub.b79 L.sub.b79 1380 L.sub.a3-418 L.sub.b79 L.sub.b79 1381 L.sub.a3-419 L.sub.b79 L.sub.b79 1382 L.sub.a3-440 L.sub.b79 L.sub.b79 1383 L.sub.a3-441 L.sub.b79 L.sub.b79 1384 L.sub.a3-446 L.sub.b79 L.sub.b79 1385 L.sub.a4-2 L.sub.b79 L.sub.b79 1386 L.sub.a4-4 L.sub.b79 L.sub.b79 1387 L.sub.a4-8 L.sub.b79 L.sub.b79 1388 L.sub.a4-10 L.sub.b79 L.sub.b79 1389 L.sub.a4-14 L.sub.b79 L.sub.b79 1390 L.sub.a4-16 L.sub.b79 L.sub.b79 1391 L.sub.a4-20 L.sub.b79 L.sub.b79 1392 L.sub.a4-22 L.sub.b79 L.sub.b79 1393 L.sub.a4-26 L.sub.b79 L.sub.b79 1394 L.sub.a4-28 L.sub.b79 L.sub.b79 1395 L.sub.a1-58 L.sub.b80 L.sub.b80 1396 L.sub.a1-88 L.sub.b80 L.sub.b80 1397 L.sub.a1-133 L.sub.b80 L.sub.b80 1398 L.sub.a1-146 L.sub.b80 L.sub.b80 1399 L.sub.a1-157 L.sub.b80 L.sub.b80 1400 L.sub.a1-158 L.sub.b80 L.sub.b80 1401 L.sub.a1-164 L.sub.b80 L.sub.b80 1402 L.sub.a1-170 L.sub.b80 L.sub.b80 1403 L.sub.a1-176 L.sub.b80 L.sub.b80 1404 L.sub.a1-208 L.sub.b80 L.sub.b80 1405 L.sub.a1-224 L.sub.b80 L.sub.b80 1406 L.sub.a1-258 L.sub.b80 L.sub.b80 1407 L.sub.a1-308 L.sub.b80 L.sub.b80 1408 L.sub.a1-321 L.sub.b80 L.sub.b80 1409 L.sub.a1-333 L.sub.b80 L.sub.b80 1410 L.sub.a1-339 L.sub.b80 L.sub.b80 1411 L.sub.a1-345 L.sub.b80 L.sub.b80 1412 L.sub.a1-382 L.sub.b80 L.sub.b80 1413 L.sub.a1-400 L.sub.b80 L.sub.b80 1414 L.sub.a1-418 L.sub.b80 L.sub.b80 1415 L.sub.a1-419 L.sub.b80 L.sub.b80 1416 L.sub.a1-440 L.sub.b80 L.sub.b80 1417 L.sub.a1-441 L.sub.b80 L.sub.b80 1418 L.sub.a1-446 L.sub.b80 L.sub.b80 1419 L.sub.a2-58 L.sub.b80 L.sub.b80 1420 L.sub.a2-88 L.sub.b80 L.sub.b80 1421 L.sub.a2-133 L.sub.b80 L.sub.b80 1422 L.sub.a2-146 L.sub.b80 L.sub.b80 1423 L.sub.a2-157 L.sub.b80 L.sub.b80 1424 L.sub.a2-158 L.sub.b80 L.sub.b80 1425 L.sub.a2-164 L.sub.b80 L.sub.b80 1426 L.sub.a2-170 L.sub.b80 L.sub.b80 1427 L.sub.a2-176 L.sub.b80 L.sub.b80 1428 L.sub.a2-208 L.sub.b80 L.sub.b80 1429 L.sub.a2-224 L.sub.b80 L.sub.b80 1430 L.sub.a2-258 L.sub.b80 L.sub.b80 1431 L.sub.a2-308 L.sub.b80 L.sub.b80 1432 L.sub.a2-321 L.sub.b80 L.sub.b80 1433 L.sub.a2-333 L.sub.b80 L.sub.b80 1434 L.sub.a2-339 L.sub.b80 L.sub.b80 1435 L.sub.a2-345 L.sub.b80 L.sub.b80 1436 L.sub.a2-382 L.sub.b80 L.sub.b80 1437 L.sub.a2-400 L.sub.b80 L.sub.b80 1438 L.sub.a2-418 L.sub.b80 L.sub.b80 1439 L.sub.a2-419 L.sub.b80 L.sub.b80 1440 L.sub.a2-440 L.sub.b80 L.sub.b80 1441 L.sub.a2-441 L.sub.b80 L.sub.b80 1442 L.sub.a2-446 L.sub.b80 L.sub.b80 1443 L.sub.a3-58 L.sub.b80 L.sub.b80 1444 L.sub.a3-88 L.sub.b80 L.sub.b80 1445 L.sub.a3-133 L.sub.b80 L.sub.b80 1446 L.sub.a3-146 L.sub.b80 L.sub.b80 1447 L.sub.a3-157 L.sub.b80 L.sub.b80 1448 L.sub.a3-158 L.sub.b80 L.sub.b80 1449 L.sub.a3-164 L.sub.b80 L.sub.b80 1450 L.sub.a3-170 L.sub.b80 L.sub.b80 1451 L.sub.a3-176 L.sub.b80 L.sub.b80 1452 L.sub.a3-208 L.sub.b80 L.sub.b80 1453 L.sub.a3-224 L.sub.b80 L.sub.b80 1454 L.sub.a3-258 L.sub.b80 L.sub.b80 1455 L.sub.a3-308 L.sub.b80 L.sub.b80 1456 L.sub.a3-321 L.sub.b80 L.sub.b80 1457 L.sub.a3-333 L.sub.b80 L.sub.b80 1458 L.sub.a3-339 L.sub.b80 L.sub.b80 1459 L.sub.a3-345 L.sub.b80 L.sub.b80 1460 L.sub.a3-382 L.sub.b80 L.sub.b80 1461 L.sub.a3-400 L.sub.b80 L.sub.b80 1462 L.sub.a3-418 L.sub.b80 L.sub.b80 1463 L.sub.a3-419 L.sub.b80 L.sub.b80 1464 L.sub.a3-440 L.sub.b80 L.sub.b80 1465 L.sub.a3-441 L.sub.b80 L.sub.b80 1466 L.sub.a3-446 L.sub.b80 L.sub.b80 1467 L.sub.a4-2 L.sub.b80 L.sub.b80 1468 L.sub.a4-4 L.sub.b80 L.sub.b80 1469 L.sub.a4-8 L.sub.b80 L.sub.b80 1470 L.sub.a4-10 L.sub.b80 L.sub.b80 1471 L.sub.a4-14 L.sub.b80 L.sub.b80 1472 L.sub.a4-16 L.sub.b80 L.sub.b80 1473 L.sub.a4-20 L.sub.b80 L.sub.b80 1474 L.sub.a4-22 L.sub.b80 L.sub.b80 1475 L.sub.a4-26 L.sub.b80 L.sub.b80 1476 L.sub.a4-28 L.sub.b80 L.sub.b80 1477 L.sub.a1-58 L.sub.b81 L.sub.b81 1478 L.sub.a1-88 L.sub.b81 L.sub.b81 1479 L.sub.a1-133 L.sub.b81 L.sub.b81 1480 L.sub.a1-146 L.sub.b81 L.sub.b81 1481 L.sub.a1-157 L.sub.b81 L.sub.b81 1482 L.sub.a1-158 L.sub.b81 L.sub.b81 1483 L.sub.a1-164 L.sub.b81 L.sub.b81 1484 L.sub.a1-170 L.sub.b81 L.sub.b81 1485 L.sub.a1-176 L.sub.b81 L.sub.b81 1486 L.sub.a1-208 L.sub.b81 L.sub.b81 1487 L.sub.a1-224 L.sub.b81 L.sub.b81 1488 L.sub.a1-258 L.sub.b81 L.sub.b81 1489 L.sub.a1-308 L.sub.b81 L.sub.b81 1490 L.sub.a1-321 L.sub.b81 L.sub.b81 1491 L.sub.a1-333 L.sub.b81 L.sub.b81 1492 L.sub.a1-339 L.sub.b81 L.sub.b81 1493 L.sub.a1-345 L.sub.b81 L.sub.b81 1494 L.sub.a1-382 L.sub.b81 L.sub.b81 1495 L.sub.a1-400 L.sub.b81 L.sub.b81 1496 L.sub.a1-418 L.sub.b81 L.sub.b81 1497 L.sub.a1-419 L.sub.b81 L.sub.b81 1498 L.sub.a1-440 L.sub.b81 L.sub.b81 1499 L.sub.a1-441 L.sub.b81 L.sub.b81 1500 L.sub.a1-446 L.sub.b81 L.sub.b81 1501 L.sub.a2-58 L.sub.b81 L.sub.b81 1502 L.sub.a2-88 L.sub.b81 L.sub.b81 1503 L.sub.a2-133 L.sub.b81 L.sub.b81 1504 L.sub.a2-146 L.sub.b81 L.sub.b81 1505 L.sub.a2-157 L.sub.b81 L.sub.b81 1506 L.sub.a2-158 L.sub.b81 L.sub.b81 1507 L.sub.a2-164 L.sub.b81 L.sub.b81 1508 L.sub.a2-170 L.sub.b81 L.sub.b81 1509 L.sub.a2-176 L.sub.b81 L.sub.b81 1510 L.sub.a2-208 L.sub.b81 L.sub.b81 1511 L.sub.a2-224 L.sub.b81 L.sub.b81 1512 L.sub.a2-258 L.sub.b81 L.sub.b81 1513 L.sub.a2-308 L.sub.b81 L.sub.b81 1514 L.sub.a2-321 L.sub.b81 L.sub.b81 1515 L.sub.a2-333 L.sub.b81 L.sub.b81 1516 L.sub.a2-339 L.sub.b81 L.sub.b81 1517 L.sub.a2-345 L.sub.b81 L.sub.b81 1518 L.sub.a2-382 L.sub.b81 L.sub.b81 1519 L.sub.a2-400 L.sub.b81 L.sub.b81 1520 L.sub.a2-418 L.sub.b81 L.sub.b81 1521 L.sub.a2-419 L.sub.b81 L.sub.b81 1522 L.sub.a2-440 L.sub.b81 L.sub.b81 1523 L.sub.a2-441 L.sub.b81 L.sub.b81 1524 L.sub.a2-446 L.sub.b81 L.sub.b81 1525 L.sub.a3-58 L.sub.b81 L.sub.b81 1526 L.sub.a3-88 L.sub.b81 L.sub.b81 1527 L.sub.a3-133 L.sub.b81 L.sub.b81 1528 L.sub.a3-146 L.sub.b81 L.sub.b81 1529 L.sub.a3-157 L.sub.b81 L.sub.b81 1530 L.sub.a3-158 L.sub.b81 L.sub.b81 1531 L.sub.a3-164 L.sub.b81 L.sub.b81 1532 L.sub.a3-170 L.sub.b81 L.sub.b81 1533 L.sub.a3-176 L.sub.b81 L.sub.b81 1534 L.sub.a3-208 L.sub.b81 L.sub.b81 1535 L.sub.a3-224 L.sub.b81 L.sub.b81 1536 L.sub.a3-258 L.sub.b81 L.sub.b81 1537 L.sub.a3-308 L.sub.b81 L.sub.b81 1538 L.sub.a3-321 L.sub.b81 L.sub.b81 1539 L.sub.a3-333 L.sub.b81 L.sub.b81 1540 L.sub.a3-339 L.sub.b81 L.sub.b81 1541 L.sub.a3-345 L.sub.b81 L.sub.b81 1542 L.sub.a3-382 L.sub.b81 L.sub.b81 1543 L.sub.a3-400 L.sub.b81 L.sub.b81 1544 L.sub.a3-418 L.sub.b81 L.sub.b81 1545 L.sub.a3-419 L.sub.b81 L.sub.b81 1546 L.sub.a3-440 L.sub.b81 L.sub.b81 1547 L.sub.a3-441 L.sub.b81 L.sub.b81 1548 L.sub.a3-446 L.sub.b81 L.sub.b81 1549 L.sub.a4-2 L.sub.b81 L.sub.b81 1550 L.sub.a4-4 L.sub.b81 L.sub.b81 1551 L.sub.a4-8 L.sub.b81 L.sub.b81 1552 L.sub.a4-10 L.sub.b81 L.sub.b81 1553 L.sub.a4-14 L.sub.b81 L.sub.b81 1554 L.sub.a4-16 L.sub.b81 L.sub.b81 1555 L.sub.a4-20 L.sub.b81 L.sub.b81 1556 L.sub.a4-22 L.sub.b81 L.sub.b81 1557 L.sub.a4-26 L.sub.b81 L.sub.b81 1558 L.sub.a4-28 L.sub.b81 L.sub.b81 1559 L.sub.a1-58 L.sub.b99 L.sub.b99 1560 L.sub.a1-88 L.sub.b99 L.sub.b99 1561 L.sub.a1-133 L.sub.b99 L.sub.b99 1562 L.sub.a1-146 L.sub.b99 L.sub.b99 1563 L.sub.a1-157 L.sub.b99 L.sub.b99 1564 L.sub.a1-158 L.sub.b99 L.sub.b99 1565 L.sub.a1-164 L.sub.b99 L.sub.b99 1566 L.sub.a1-170 L.sub.b99 L.sub.b99 1567 L.sub.a1-176 L.sub.b99 L.sub.b99 1568 L.sub.a1-208 L.sub.b99 L.sub.b99 1569 L.sub.a1-224 L.sub.b99 L.sub.b99 1570 L.sub.a1-258 L.sub.b99 L.sub.b99 1571 L.sub.a1-308 L.sub.b99 L.sub.b99 1572 L.sub.a1-321 L.sub.b99 L.sub.b99 1573 L.sub.a1-333 L.sub.b99 L.sub.b99 1574 L.sub.a1-339 L.sub.b99 L.sub.b99 1575 L.sub.a1-345 L.sub.b99 L.sub.b99 1576 L.sub.a1-382 L.sub.b99 L.sub.b99 1577 L.sub.a1-400 L.sub.b99 L.sub.b99 1578 L.sub.a1-418 L.sub.b99 L.sub.b99 1579 L.sub.a1-419 L.sub.b99 L.sub.b99 1580 L.sub.a1-440 L.sub.b99 L.sub.b99 1581 L.sub.a1-441 L.sub.b99 L.sub.b99 1582 L.sub.a1-446 L.sub.b99 L.sub.b99 1583 L.sub.a2-58 L.sub.b99 L.sub.b99 1584 L.sub.a2-88 L.sub.b99 L.sub.b99 1585 L.sub.a2-133 L.sub.b99 L.sub.b99 1586 L.sub.a2-146 L.sub.b99 L.sub.b99 1587 L.sub.a2-157 L.sub.b99 L.sub.b99 1588 L.sub.a2-158 L.sub.b99 L.sub.b99 1589 L.sub.a2-164 L.sub.b99 L.sub.b99 1590 L.sub.a2-170 L.sub.b99 L.sub.b99 1591 L.sub.a2-176 L.sub.b99 L.sub.b99 1592 L.sub.a2-208 L.sub.b99 L.sub.b99 1593 L.sub.a2-224 L.sub.b99 L.sub.b99 1594 L.sub.a2-258 L.sub.b99 L.sub.b99 1595 L.sub.a2-308 L.sub.b99 L.sub.b99 1596 L.sub.a2-321 L.sub.b99 L.sub.b99 1597 L.sub.a2-333 L.sub.b99 L.sub.b99 1598 L.sub.a2-339 L.sub.b99 L.sub.b99 1599 L.sub.a2-345 L.sub.b99 L.sub.b99 1600 L.sub.a2-382 L.sub.b99 L.sub.b99 1601 L.sub.a2-400 L.sub.b99 L.sub.b99 1602 L.sub.a2-418 L.sub.b99 L.sub.b99 1603 L.sub.a2-419 L.sub.b99 L.sub.b99 1604 L.sub.a2-440 L.sub.b99 L.sub.b99 1605 L.sub.a2-441 L.sub.b99 L.sub.b99 1606 L.sub.a2-446 L.sub.b99 L.sub.b99 1607 L.sub.a3-58 L.sub.b99 L.sub.b99 1608 L.sub.a3-88 L.sub.b99 L.sub.b99 1609 L.sub.a3-133 L.sub.b99 L.sub.b99 1610 L.sub.a3-146 L.sub.b99 L.sub.b99 1611 L.sub.a3-157 L.sub.b99 L.sub.b99 1612 L.sub.a3-158 L.sub.b99 L.sub.b99 1613 L.sub.a3-164 L.sub.b99 L.sub.b99 1614 L.sub.a3-170 L.sub.b99 L.sub.b99 1615 L.sub.a3-176 L.sub.b99 L.sub.b99 1616 L.sub.a3-208 L.sub.b99 L.sub.b99 1617 L.sub.a3-224 L.sub.b99 L.sub.b99 1618 L.sub.a3-258 L.sub.b99 L.sub.b99 1619 L.sub.a3-308 L.sub.b99 L.sub.b99 1620 L.sub.a3-321 L.sub.b99 L.sub.b99 1621 L.sub.a3-333 L.sub.b99 L.sub.b99 1622 L.sub.a3-339 L.sub.b99 L.sub.b99 1623 L.sub.a3-345 L.sub.b99 L.sub.b99 1624 L.sub.a3-382 L.sub.b99 L.sub.b99 1625 L.sub.a3-400 L.sub.b99 L.sub.b99 1626 L.sub.a3-418 L.sub.b99 L.sub.b99 1627 L.sub.a3-419 L.sub.b99 L.sub.b99 1628 L.sub.a3-440 L.sub.b99 L.sub.b99 1629 L.sub.a3-441 L.sub.b99 L.sub.b99 1630 L.sub.a3-446 L.sub.b99 L.sub.b99 1631 L.sub.a4-2 L.sub.b99 L.sub.b99 1632 L.sub.a4-4 L.sub.b99 L.sub.b99 1633 L.sub.a4-8 L.sub.b99 L.sub.b99 1634 L.sub.a4-10 L.sub.b99 L.sub.b99 1635 L.sub.a4-14 L.sub.b99 L.sub.b99 1636 L.sub.a4-16 L.sub.b99 L.sub.b99 1637 L.sub.a4-20 L.sub.b99 L.sub.b99 1638 L.sub.a4-22 L.sub.b99 L.sub.b99 1639 L.sub.a4-26 L.sub.b99 L.sub.b99 1640 L.sub.a4-28 L.sub.b99 L.sub.b99 1641 L.sub.a1-58 L.sub.b112 L.sub.b112 1642 L.sub.a1-88 L.sub.b112 L.sub.b112 1643 L.sub.a1-133 L.sub.b112 L.sub.b112 1644 L.sub.a1-146 L.sub.b112 L.sub.b112 1645 L.sub.a1-157 L.sub.b112 L.sub.b112 1646 L.sub.a1-158 L.sub.b112 L.sub.b112 1647 L.sub.a1-164 L.sub.b112 L.sub.b112 1648 L.sub.a1-170 L.sub.b112 L.sub.b112 1649 L.sub.a1-176 L.sub.b112 L.sub.b112 1650 L.sub.a1-208 L.sub.b112 L.sub.b112 1651 L.sub.a1-224 L.sub.b112 L.sub.b112 1652 L.sub.a1-258 L.sub.b112 L.sub.b112 1653 L.sub.a1-308 L.sub.b112 L.sub.b112 1654 L.sub.a1-321 L.sub.b112 L.sub.b112 1655 L.sub.a1-333 L.sub.b112 L.sub.b112 1656 L.sub.a1-339 L.sub.b112 L.sub.b112 1657 L.sub.a1-345 L.sub.b112 L.sub.b112 1658 L.sub.a1-382 L.sub.b112 L.sub.b112 1659 L.sub.a1-400 L.sub.b112 L.sub.b112 1660 L.sub.a1-418 L.sub.b112 L.sub.b112 1661 L.sub.a1-419 L.sub.b112 L.sub.b112 1662 L.sub.a1-440 L.sub.b112 L.sub.b112 1663 L.sub.a1-441 L.sub.b112 L.sub.b112 1664 L.sub.a1-446 L.sub.b112 L.sub.b112 1665 L.sub.a2-58 L.sub.b112 L.sub.b112 1666 L.sub.a2-88 L.sub.b112 L.sub.b112 1667 L.sub.a2-133 L.sub.b112 L.sub.b112 1668 L.sub.a2-146 L.sub.b112 L.sub.b112 1669 L.sub.a2-157 L.sub.b112 L.sub.b112 1670 L.sub.a2-158 L.sub.b112 L.sub.b112 1671 L.sub.a2-164 L.sub.b112 L.sub.b112 1672 L.sub.a2-170 L.sub.b112 L.sub.b112 1673 L.sub.a2-176 L.sub.b112 L.sub.b112 1674 L.sub.a2-208 L.sub.b112 L.sub.b112 1675 L.sub.a2-224 L.sub.b112 L.sub.b112 1676 L.sub.a2-258 L.sub.b112 L.sub.b112 1677 L.sub.a2-308 L.sub.b112 L.sub.b112 1678 L.sub.a2-321 L.sub.b112 L.sub.b112 1679 L.sub.a2-333 L.sub.b112 L.sub.b112 1680 L.sub.a2-339 L.sub.b112 L.sub.b112 1681 L.sub.a2-345 L.sub.b112 L.sub.b112 1682 L.sub.a2-382 L.sub.b112 L.sub.b112 1683 L.sub.a2-400 L.sub.b112 L.sub.b112 1684 L.sub.a2-418 L.sub.b112 L.sub.b112 1685 L.sub.a2-419 L.sub.b112 L.sub.b112 1686 L.sub.a2-440 L.sub.b112 L.sub.b112 1687 L.sub.a2-441 L.sub.b112 L.sub.b112 1688 L.sub.a2-446 L.sub.b112 L.sub.b112 1689 L.sub.a3-58 L.sub.b112 L.sub.b112 1690 L.sub.a3-88 L.sub.b112 L.sub.b112 1691 L.sub.a3-133 L.sub.b112 L.sub.b112 1692 L.sub.a3-146 L.sub.b112 L.sub.b112 1693 L.sub.a3-157 L.sub.b112 L.sub.b112 1694 L.sub.a3-158 L.sub.b112 L.sub.b112 1695 L.sub.a3-164 L.sub.b112 L.sub.b112 1696 L.sub.a3-170 L.sub.b112 L.sub.b112 1697 L.sub.a3-176 L.sub.b112 L.sub.b112 1698 L.sub.a3-208 L.sub.b112 L.sub.b112 1699 L.sub.a3-224 L.sub.b112 L.sub.b112 1700 L.sub.a3-258 L.sub.b112 L.sub.b112 1701 L.sub.a3-308 L.sub.b112 L.sub.b112 1702 L.sub.a3-321 L.sub.b112 L.sub.b112 1703 L.sub.a3-333 L.sub.b112 L.sub.b112 1704 L.sub.a3-339 L.sub.b112 L.sub.b112 1705 L.sub.a3-345 L.sub.b112 L.sub.b112 1706 L.sub.a3-382 L.sub.b112 L.sub.b112 1707 L.sub.a3-400 L.sub.b112 L.sub.b112 1708 L.sub.a3-418 L.sub.b112 L.sub.b112 1709 L.sub.a3-419 L.sub.b112 L.sub.b112 1710 L.sub.a3-440 L.sub.b112 L.sub.b112 1711 L.sub.a3-441 L.sub.b112 L.sub.b112 1712 L.sub.a3-446 L.sub.b112 L.sub.b112 1713 L.sub.a4-2 L.sub.b112 L.sub.b112 1714 L.sub.a4-4 L.sub.b112 L.sub.b112 1715 L.sub.a4-8 L.sub.b112 L.sub.b112 1716 L.sub.a4-10 L.sub.b112 L.sub.b112 1717 L.sub.a4-14 L.sub.b112 L.sub.b112 1718 L.sub.a4-16 L.sub.b112 L.sub.b112 1719 L.sub.a4-20 L.sub.b112 L.sub.b112 1720 L.sub.a4-22 L.sub.b112 L.sub.b112 1721 L.sub.a4-26 L.sub.b112 L.sub.b112 1722 L.sub.a4-28 L.sub.b112 L.sub.b112 1723 L.sub.a1-58 L.sub.b151 L.sub.b151 1724 L.sub.a1-88 L.sub.b151 L.sub.b151 1725 L.sub.a1-133 L.sub.b151 L.sub.b151 1726 L.sub.a1-146 L.sub.b151 L.sub.b151 1727 L.sub.a1-157 L.sub.b151 L.sub.b151 1728 L.sub.a1-158 L.sub.b151 L.sub.b151 1729 L.sub.a1-164 L.sub.b151 L.sub.b151 1730 L.sub.a1-170 L.sub.b151 L.sub.b151 1731 L.sub.a1-176 L.sub.b151 L.sub.b151 1732 L.sub.a1-208 L.sub.b151 L.sub.b151 1733 L.sub.a1-224 L.sub.b151 L.sub.b151 1734 L.sub.a1-258 L.sub.b151 L.sub.b151 1735 L.sub.a1-308 L.sub.b151 L.sub.b151 1736 L.sub.a1-321 L.sub.b151 L.sub.b151 1737 L.sub.a1-333 L.sub.b151 L.sub.b151 1738 L.sub.a1-339 L.sub.b151 L.sub.b151 1739 L.sub.a1-345 L.sub.b151 L.sub.b151 1740 L.sub.a1-382 L.sub.b151 L.sub.b151 1741 L.sub.a1-400 L.sub.b151 L.sub.b151 1742 L.sub.a1-418 L.sub.b151 L.sub.b151 1743 L.sub.a1-419 L.sub.b151 L.sub.b151 1744 L.sub.a1-440 L.sub.b151 L.sub.b151 1745 L.sub.a1-441 L.sub.b151 L.sub.b151 1746 L.sub.a1-446 L.sub.b151 L.sub.b151 1747 L.sub.a2-58 L.sub.b151 L.sub.b151 1748 L.sub.a2-88 L.sub.b151 L.sub.b151 1749 L.sub.a2-133 L.sub.b151 L.sub.b151 1750 L.sub.a2-146 L.sub.b151 L.sub.b151 1751 L.sub.a2-157 L.sub.b151 L.sub.b151 1752 L.sub.a2-158 L.sub.b151 L.sub.b151 1753 L.sub.a2-164 L.sub.b151 L.sub.b151 1754 L.sub.a2-170 L.sub.b151 L.sub.b151 1755 L.sub.a2-176 L.sub.b151 L.sub.b151 1756 L.sub.a2-208 L.sub.b151 L.sub.b151 1757 L.sub.a2-224 L.sub.b151 L.sub.b151 1758 L.sub.a2-258 L.sub.b151 L.sub.b151 1759 L.sub.a2-308 L.sub.b151 L.sub.b151 1760 L.sub.a2-321 L.sub.b151 L.sub.b151 1761 L.sub.a2-333 L.sub.b151 L.sub.b151 1762 L.sub.a2-339 L.sub.b151 L.sub.b151 1763 L.sub.a2-345 L.sub.b151 L.sub.b151 1764 L.sub.a2-382 L.sub.b151 L.sub.b151 1765 L.sub.a2-400 L.sub.b151 L.sub.b151 1766 L.sub.a2-418 L.sub.b151 L.sub.b151 1767 L.sub.a2-419 L.sub.b151 L.sub.b151 1768 L.sub.a2-440 L.sub.b151 L.sub.b151 1769 L.sub.a2-441 L.sub.b151 L.sub.b151 1770 L.sub.a2-446 L.sub.b151 L.sub.b151 1771 L.sub.a3-58 L.sub.b151 L.sub.b151 1772 L.sub.a3-88 L.sub.b151 L.sub.b151 1773 L.sub.a3-133 L.sub.b151 L.sub.b151 1774 L.sub.a3-146 L.sub.b151 L.sub.b151 1775 L.sub.a3-157 L.sub.b151 L.sub.b151 1776 L.sub.a3-158 L.sub.b151 L.sub.b151 1777 L.sub.a3-164 L.sub.b151 L.sub.b151 1778 L.sub.a3-170 L.sub.b151 L.sub.b151 1779 L.sub.a3-176 L.sub.b151 L.sub.b151 1780 L.sub.a3-208 L.sub.b151 L.sub.b151 1781 L.sub.a3-224 L.sub.b151 L.sub.b151 1782 L.sub.a3-258 L.sub.b151 L.sub.b151 1783 L.sub.a3-308 L.sub.b151 L.sub.b151 1784 L.sub.a3-321 L.sub.b151 L.sub.b151 1785 L.sub.a3-333 L.sub.b151 L.sub.b151 1786 L.sub.a3-339 L.sub.b151 L.sub.b151 1787 L.sub.a3-345 L.sub.b151 L.sub.b151 1788 L.sub.a3-382 L.sub.b151 L.sub.b151 1789 L.sub.a3-400 L.sub.b151 L.sub.b151 1790 L.sub.a3-418 L.sub.b151 L.sub.b151 1791 L.sub.a3-419 L.sub.b151 L.sub.b151 1792 L.sub.a3-440 L.sub.b151 L.sub.b151 1793 L.sub.a3-441 L.sub.b151 L.sub.b151 1794 L.sub.a3-446 L.sub.b151 L.sub.b151 1795 L.sub.a4-2 L.sub.b151 L.sub.b151 1796 L.sub.a4-4 L.sub.b151 L.sub.b151 1797 L.sub.a4-8 L.sub.b151 L.sub.b151 1798 L.sub.a4-10 L.sub.b151 L.sub.b151 1799 L.sub.a4-14 L.sub.b151 L.sub.b151 1800 L.sub.a4-16 L.sub.b151 L.sub.b151 1801 L.sub.a4-20 L.sub.b151 L.sub.b151 1802 L.sub.a4-22 L.sub.b151 L.sub.b151 1803 L.sub.a4-26 L.sub.b151 L.sub.b151 1804 L.sub.a4-28 L.sub.b151 L.sub.b151 1805 L.sub.a1-58 L.sub.b153 L.sub.b153 1806 L.sub.a1-88 L.sub.b153 L.sub.b153 1807 L.sub.a1-133 L.sub.b153 L.sub.b153 1808 L.sub.a1-146 L.sub.b153 L.sub.b153 1809 L.sub.a1-157 L.sub.b153 L.sub.b153 1810 L.sub.a1-158 L.sub.b153 L.sub.b153 1811 L.sub.a1-164 L.sub.b153 L.sub.b153 1812 L.sub.a1-170 L.sub.b153 L.sub.b153 1813 L.sub.a1-176 L.sub.b153 L.sub.b153 1814 L.sub.a1-208 L.sub.b153 L.sub.b153 1815 L.sub.a1-224 L.sub.b153 L.sub.b153 1816 L.sub.a1-258 L.sub.b153 L.sub.b153 1817 L.sub.a1-308 L.sub.b153 L.sub.b153 1818 L.sub.a1-321 L.sub.b153 L.sub.b153 1819 L.sub.a1-333 L.sub.b153 L.sub.b153 1820 L.sub.a1-339 L.sub.b153 L.sub.b153 1821 L.sub.a1-345 L.sub.b153 L.sub.b153 1822 L.sub.a1-382 L.sub.b153 L.sub.b153 1823 L.sub.a1-400 L.sub.b153 L.sub.b153 1824 L.sub.a1-418 L.sub.b153 L.sub.b153 1825 L.sub.a1-419 L.sub.b153 L.sub.b153 1826 L.sub.a1-440 L.sub.b153 L.sub.b153 1827 L.sub.a1-441 L.sub.b153 L.sub.b153 1828 L.sub.a1-446 L.sub.b153 L.sub.b153 1829 L.sub.a2-58 L.sub.b153 L.sub.b153 1830 L.sub.a2-88 L.sub.b153 L.sub.b153 1831 L.sub.a2-133 L.sub.b153 L.sub.b153 1832 L.sub.a2-146 L.sub.b153 L.sub.b153 1833 L.sub.a2-157 L.sub.b153 L.sub.b153 1834 L.sub.a2-158 L.sub.b153 L.sub.b153 1835 L.sub.a2-164 L.sub.b153 L.sub.b153 1836 L.sub.a2-170 L.sub.b153 L.sub.b153 1837 L.sub.a2-176 L.sub.b153 L.sub.b153 1838 L.sub.a2-208 L.sub.b153 L.sub.b153 1839 L.sub.a2-224 L.sub.b153 L.sub.b153 1840 L.sub.a2-258 L.sub.b153 L.sub.b153 1841 L.sub.a2-308 L.sub.b153 L.sub.b153 1842 L.sub.a2-321 L.sub.b153 L.sub.b153 1843 L.sub.a2-333 L.sub.b153 L.sub.b153 1844 L.sub.a2-339 L.sub.b153 L.sub.b153 1845 L.sub.a2-345 L.sub.b153 L.sub.b153 1846 L.sub.a2-382 L.sub.b153 L.sub.b153 1847 L.sub.a2-400 L.sub.b153 L.sub.b153 1848 L.sub.a2-418 L.sub.b153 L.sub.b153 1849 L.sub.a2-419 L.sub.b153 L.sub.b153 1850 L.sub.a2-440 L.sub.b153 L.sub.b153 1851 L.sub.a2-441 L.sub.b153 L.sub.b153 1852 L.sub.a2-446 L.sub.b153 L.sub.b153 1853 L.sub.a3-58 L.sub.b153 L.sub.b153 1854 L.sub.a3-88 L.sub.b153 L.sub.b153 1855 L.sub.a3-133 L.sub.b153 L.sub.b153 1856 L.sub.a3-146 L.sub.b153 L.sub.b153 1857 L.sub.a3-157 L.sub.b153 L.sub.b153 1858 L.sub.a3-158 L.sub.b153 L.sub.b153 1859 L.sub.a3-164 L.sub.b153 L.sub.b153 1860 L.sub.a3-170 L.sub.b153 L.sub.b153 1861 L.sub.a3-176 L.sub.b153 L.sub.b153 1862 L.sub.a3-208 L.sub.b153 L.sub.b153 1863 L.sub.a3-224 L.sub.b153 L.sub.b153 1864 L.sub.a3-258 L.sub.b153 L.sub.b153 1865 L.sub.a3-308 L.sub.b153 L.sub.b153 1866 L.sub.a3-321 L.sub.b153 L.sub.b153 1867 L.sub.a3-333 L.sub.b153 L.sub.b153 1868 L.sub.a3-339 L.sub.b153 L.sub.b153 1869 L.sub.a3-345 L.sub.b153 L.sub.b153 1870 L.sub.a3-382 L.sub.b153 L.sub.b153 1871 L.sub.a3-400 L.sub.b153 L.sub.b153 1872 L.sub.a3-418 L.sub.b153 L.sub.b153 1873 L.sub.a3-419 L.sub.b153 L.sub.b153 1874 L.sub.a3-440 L.sub.b153 L.sub.b153 1875 L.sub.a3-441 L.sub.b153 L.sub.b153 1876 L.sub.a3-446 L.sub.b153 L.sub.b153 1877 L.sub.a4-2 L.sub.b153 L.sub.b153 1878 L.sub.a4-4 L.sub.b153 L.sub.b153 1879 L.sub.a4-8 L.sub.b153 L.sub.b153 1880 L.sub.a4-10 L.sub.b153 L.sub.b153 1881 L.sub.a4-14 L.sub.b153 L.sub.b153 1882 L.sub.a4-16 L.sub.b153 L.sub.b153 1883 L.sub.a4-20 L.sub.b153 L.sub.b153 1884 L.sub.a4-22 L.sub.b153 L.sub.b153 1885 L.sub.a4-26 L.sub.b153 L.sub.b153 1886 L.sub.a4-28 L.sub.b153 L.sub.b153 1887 L.sub.a1-58 L.sub.b164 L.sub.b164 1888 L.sub.a1-88 L.sub.b164 L.sub.b164 1889 L.sub.a1-133 L.sub.b164 L.sub.b164 1890 L.sub.a1-146 L.sub.b164 L.sub.b164 1891 L.sub.a1-157 L.sub.b164 L.sub.b164 1892 L.sub.a1-158 L.sub.b164 L.sub.b164 1893 L.sub.a1-164 L.sub.b164 L.sub.b164 1894 L.sub.a1-170 L.sub.b164 L.sub.b164 1895 L.sub.a1-176 L.sub.b164 L.sub.b164 1896 L.sub.a1-208 L.sub.b164 L.sub.b164 1897 L.sub.a1-224 L.sub.b164 L.sub.b164 1898 L.sub.a1-258 L.sub.b164 L.sub.b164 1899 L.sub.a1-308 L.sub.b164 L.sub.b164 1900 L.sub.a1-321 L.sub.b164 L.sub.b164 1901 L.sub.a1-333 L.sub.b164 L.sub.b164 1902 L.sub.a1-339 L.sub.b164 L.sub.b164 1903 L.sub.a1-345 L.sub.b164 L.sub.b164 1904 L.sub.a1-382 L.sub.b164 L.sub.b164 1905 L.sub.a1-400 L.sub.b164 L.sub.b164 1906 L.sub.a1-418 L.sub.b164 L.sub.b164 1907 L.sub.a1-419 L.sub.b164 L.sub.b164 1908 L.sub.a1-440 L.sub.b164 L.sub.b164 1909 L.sub.a1-441 L.sub.b164 L.sub.b164 1910 L.sub.a1-446 L.sub.b164 L.sub.b164 1911 L.sub.a2-58 L.sub.b164 L.sub.b164 1912 L.sub.a2-88 L.sub.b164 L.sub.b164 1913 L.sub.a2-133 L.sub.b164 L.sub.b164 1914 L.sub.a2-146 L.sub.b164 L.sub.b164 1915 L.sub.a2-157 L.sub.b164 L.sub.b164 1916 L.sub.a2-158 L.sub.b164 L.sub.b164 1917 L.sub.a2-164 L.sub.b164 L.sub.b164 1918 L.sub.a2-170 L.sub.b164 L.sub.b164 1919 L.sub.a2-176 L.sub.b164 L.sub.b164 1920 L.sub.a2-208 L.sub.b164 L.sub.b164 1921 L.sub.a2-224 L.sub.b164 L.sub.b164 1922 L.sub.a2-258 L.sub.b164 L.sub.b164 1923 L.sub.a2-308 L.sub.b164 L.sub.b164 1924 L.sub.a2-321 L.sub.b164 L.sub.b164 1925 L.sub.a2-333 L.sub.b164 L.sub.b164 1926 L.sub.a2-339 L.sub.b164 L.sub.b164 1927 L.sub.a2-345 L.sub.b164 L.sub.b164 1928 L.sub.a2-382 L.sub.b164 L.sub.b164 1929 L.sub.a2-400 L.sub.b164 L.sub.b164 1930 L.sub.a2-418 L.sub.b164 L.sub.b164 1931 L.sub.a2-419 L.sub.b164 L.sub.b164 1932 L.sub.a2-440 L.sub.b164 L.sub.b164 1933 L.sub.a2-441 L.sub.b164 L.sub.b164 1934 L.sub.a2-446 L.sub.b164 L.sub.b164 1935 L.sub.a3-58 L.sub.b164 L.sub.b164 1936 L.sub.a3-88 L.sub.b164 L.sub.b164 1937 L.sub.a3-133 L.sub.b164 L.sub.b164 1938 L.sub.a3-146 L.sub.b164 L.sub.b164 1939 L.sub.a3-157 L.sub.b164 L.sub.b164 1940 L.sub.a3-158 L.sub.b164 L.sub.b164 1941 L.sub.a3-164 L.sub.b164 L.sub.b164 1942 L.sub.a3-170 L.sub.b164 L.sub.b164 1943 L.sub.a3-176 L.sub.b164 L.sub.b164 1944 L.sub.a3-208 L.sub.b164 L.sub.b164 1945 L.sub.a3-224 L.sub.b164 L.sub.b164 1946 L.sub.a3-258 L.sub.b164 L.sub.b164 1947 L.sub.a3-308 L.sub.b164 L.sub.b164 1948 L.sub.a3-321 L.sub.b164 L.sub.b164 1949 L.sub.a3-333 L.sub.b164 L.sub.b164 1950 L.sub.a3-339 L.sub.b164 L.sub.b164 1951 L.sub.a3-345 L.sub.b164 L.sub.b164 1952 L.sub.a3-382 L.sub.b164 L.sub.b164 1953 L.sub.a3-400 L.sub.b164 L.sub.b164 1954 L.sub.a3-418 L.sub.b164 L.sub.b164 1955 L.sub.a3-419 L.sub.b164 L.sub.b164 1956 L.sub.a3-440 L.sub.b164 L.sub.b164 1957 L.sub.a3-441 L.sub.b164 L.sub.b164 1958 L.sub.a3-446 L.sub.b164 L.sub.b164 1959 L.sub.a4-2 L.sub.b164 L.sub.b164 1960 L.sub.a4-4 L.sub.b164 L.sub.b164 1961 L.sub.a4-8 L.sub.b164 L.sub.b164 1962 L.sub.a4-10 L.sub.b164 L.sub.b164 1963 L.sub.a4-14 L.sub.b164 L.sub.b164 1964 L.sub.a4-16 L.sub.b164 L.sub.b164 1965 L.sub.a4-20 L.sub.b164 L.sub.b164 1966 L.sub.a4-22 L.sub.b164 L.sub.b164 1967 L.sub.a4-26 L.sub.b164 L.sub.b164 1968 L.sub.a4-28 L.sub.b164 L.sub.b164 1969 L.sub.a1-58 L.sub.b166 L.sub.b166 1970 L.sub.a1-88 L.sub.b166 L.sub.b166 1971 L.sub.a1-133 L.sub.b166 L.sub.b166 1972 L.sub.a1-146 L.sub.b166 L.sub.b166 1973 L.sub.a1-157 L.sub.b166 L.sub.b166 1974 L.sub.a1-158 L.sub.b166 L.sub.b166 1975 L.sub.a1-164 L.sub.b166 L.sub.b166 1976 L.sub.a1-170 L.sub.b166 L.sub.b166 1977 L.sub.a1-176 L.sub.b166 L.sub.b166 1978 L.sub.a1-208 L.sub.b166 L.sub.b166 1979 L.sub.a1-224 L.sub.b166 L.sub.b166 1980 L.sub.a1-258 L.sub.b166 L.sub.b166 1981 L.sub.a1-308 L.sub.b166 L.sub.b166 1982 L.sub.a1-321 L.sub.b166 L.sub.b166 1983 L.sub.a1-333 L.sub.b166 L.sub.b166 1984 L.sub.a1-339 L.sub.b166 L.sub.b166 1985 L.sub.a1-345 L.sub.b166 L.sub.b166 1986 L.sub.a1-382 L.sub.b166 L.sub.b166 1987 L.sub.a1-400 L.sub.b166 L.sub.b166 1988 L.sub.a1-418 L.sub.b166 L.sub.b166 1989 L.sub.a1-419 L.sub.b166 L.sub.b166 1990 L.sub.a1-440 L.sub.b166 L.sub.b166 1991 L.sub.a1-441 L.sub.b166 L.sub.b166 1992 L.sub.a1-446 L.sub.b166 L.sub.b166 1993 L.sub.a2-58 L.sub.b166 L.sub.b166 1994 L.sub.a2-88 L.sub.b166 L.sub.b166 1995 L.sub.a2-133 L.sub.b166 L.sub.b166 1996 L.sub.a2-146 L.sub.b166 L.sub.b166 1997 L.sub.a2-157 L.sub.b166 L.sub.b166 1998 L.sub.a2-158 L.sub.b166 L.sub.b166 1999 L.sub.a2-164 L.sub.b166 L.sub.b166 2000 L.sub.a2-170 L.sub.b166 L.sub.b166 2001 L.sub.a2-176 L.sub.b166 L.sub.b166 2002 L.sub.a2-208 L.sub.b166 L.sub.b166 2003 L.sub.a2-224 L.sub.b166 L.sub.b166 2004 L.sub.a2-258 L.sub.b166 L.sub.b166 2005 L.sub.a2-308 L.sub.b166 L.sub.b166 2006 L.sub.a2-321 L.sub.b166 L.sub.b166 2007 L.sub.a2-333 L.sub.b166 L.sub.b166 2008 L.sub.a2-339 L.sub.b166 L.sub.b166 2009 L.sub.a2-345 L.sub.b166 L.sub.b166 2010 L.sub.a2-382 L.sub.b166 L.sub.b166 2011 L.sub.a2-400 L.sub.b166 L.sub.b166 2012 L.sub.a2-418 L.sub.b166 L.sub.b166 2013 L.sub.a2-419 L.sub.b166 L.sub.b166 2014 L.sub.a2-440 L.sub.b166 L.sub.b166 2015 L.sub.a2-441 L.sub.b166 L.sub.b166 2016 L.sub.a2-446 L.sub.b166 L.sub.b166 2017 L.sub.a3-58 L.sub.b166 L.sub.b166 2018 L.sub.a3-88 L.sub.b166 L.sub.b166 2019 L.sub.a3-133 L.sub.b166 L.sub.b166 2020 L.sub.a3-146 L.sub.b166 L.sub.b166 2021 L.sub.a3-157 L.sub.b166 L.sub.b166 2022 L.sub.a3-158 L.sub.b166 L.sub.b166 2023 L.sub.a3-164 L.sub.b166 L.sub.b166 2024 L.sub.a3-170 L.sub.b166 L.sub.b166 2025 L.sub.a3-176 L.sub.b166 L.sub.b166 2026 L.sub.a3-208 L.sub.b166 L.sub.b166 2027 L.sub.a3-224 L.sub.b166 L.sub.b166 2028 L.sub.a3-258 L.sub.b166 L.sub.b166 2029 L.sub.a3-308 L.sub.b166 L.sub.b166 2030 L.sub.a3-321 L.sub.b166 L.sub.b166 2031 L.sub.a3-333 L.sub.b166 L.sub.b166 2032 L.sub.a3-339 L.sub.b166 L.sub.b166 2033 L.sub.a3-345 L.sub.b166 L.sub.b166 2034 L.sub.a3-382 L.sub.b166 L.sub.b166 2035 L.sub.a3-400 L.sub.b166 L.sub.b166 2036 L.sub.a3-418 L.sub.b166 L.sub.b166 2037 L.sub.a3-419 L.sub.b166 L.sub.b166 2038 L.sub.a3-440 L.sub.b166 L.sub.b166 2039 L.sub.a3-441 L.sub.b166 L.sub.b166 2040 L.sub.a3-446 L.sub.b166 L.sub.b166 2041 L.sub.a4-2 L.sub.b166 L.sub.b166 2042 L.sub.a4-4 L.sub.b166 L.sub.b166 2043 L.sub.a4-8 L.sub.b166 L.sub.b166 2044 L.sub.a4-10 L.sub.b166 L.sub.b166 2045 L.sub.a4-14 L.sub.b166 L.sub.b166 2046 L.sub.a4-16 L.sub.b166 L.sub.b166 2047 L.sub.a4-20 L.sub.b166 L.sub.b166 2048 L.sub.a4-22 L.sub.b166 L.sub.b166 2049 L.sub.a4-26 L.sub.b166 L.sub.b166 2050 L.sub.a4-28 L.sub.b166 L.sub.b166 2051 L.sub.a1-58 L.sub.b209 L.sub.b209 2052 L.sub.a1-88 L.sub.b209 L.sub.b209 2053 L.sub.a1-133 L.sub.b209 L.sub.b209 2054 L.sub.a1-146 L.sub.b209 L.sub.b209 2055 L.sub.a1-157 L.sub.b209 L.sub.b209 2056 L.sub.a1-158 L.sub.b209 L.sub.b209 2057 L.sub.a1-164 L.sub.b209 L.sub.b209 2058 L.sub.a1-170 L.sub.b209 L.sub.b209 2059 L.sub.a1-176 L.sub.b209 L.sub.b209 2060 L.sub.a1-208 L.sub.b209 L.sub.b209 2061 L.sub.a1-224 L.sub.b209 L.sub.b209 2062 L.sub.a1-258 L.sub.b209 L.sub.b209 2063 L.sub.a1-308 L.sub.b209 L.sub.b209 2064 L.sub.a1-321 L.sub.b209 L.sub.b209 2065 L.sub.a1-333 L.sub.b209 L.sub.b209 2066 L.sub.a1-339 L.sub.b209 L.sub.b209 2067 L.sub.a1-345 L.sub.b209 L.sub.b209 2068 L.sub.a1-382 L.sub.b209 L.sub.b209 2069 L.sub.a1-400 L.sub.b209 L.sub.b209 2070 L.sub.a1-418 L.sub.b209 L.sub.b209 2071 L.sub.a1-419 L.sub.b209 L.sub.b209 2072 L.sub.a1-440 L.sub.b209 L.sub.b209 2073 L.sub.a1-441 L.sub.b209 L.sub.b209 2074 L.sub.a1-446 L.sub.b209 L.sub.b209 2075 L.sub.a2-58 L.sub.b209 L.sub.b209 2076 L.sub.a2-88 L.sub.b209 L.sub.b209 2077 L.sub.a2-133 L.sub.b209 L.sub.b209 2078 L.sub.a2-146 L.sub.b209 L.sub.b209 2079 L.sub.a2-157 L.sub.b209 L.sub.b209 2080 L.sub.a2-158 L.sub.b209 L.sub.b209 2081 L.sub.a2-164 L.sub.b209 L.sub.b209 2082 L.sub.a2-170 L.sub.b209 L.sub.b209 2083 L.sub.a2-176 L.sub.b209 L.sub.b209 2084 L.sub.a2-208 L.sub.b209 L.sub.b209 2085 L.sub.a2-224 L.sub.b209 L.sub.b209 2086 L.sub.a2-258 L.sub.b209 L.sub.b209 2087 L.sub.a2-308 L.sub.b209 L.sub.b209 2088 L.sub.a2-321 L.sub.b209 L.sub.b209 2089 L.sub.a2-333 L.sub.b209 L.sub.b209 2090 L.sub.a2-339 L.sub.b209 L.sub.b209 2091 L.sub.a2-345 L.sub.b209 L.sub.b209 2092 L.sub.a2-382 L.sub.b209 L.sub.b209 2093 L.sub.a2-400 L.sub.b209 L.sub.b209 2094 L.sub.a2-418 L.sub.b209 L.sub.b209 2095 L.sub.a2-419 L.sub.b209 L.sub.b209 2096 L.sub.a2-440 L.sub.b209 L.sub.b209 2097 L.sub.a2-441 L.sub.b209 L.sub.b209 2098 L.sub.a2-446 L.sub.b209 L.sub.b209 2099 L.sub.a3-58 L.sub.b209 L.sub.b209 2100 L.sub.a3-88 L.sub.b209 L.sub.b209 2101 L.sub.a3-133 L.sub.b209 L.sub.b209 2102 L.sub.a3-146 L.sub.b209 L.sub.b209 2103 L.sub.a3-157 L.sub.b209 L.sub.b209 2104 L.sub.a3-158 L.sub.b209 L.sub.b209 2105 L.sub.a3-164 L.sub.b209 L.sub.b209 2106 L.sub.a3-170 L.sub.b209 L.sub.b209 2107 L.sub.a3-176 L.sub.b209 L.sub.b209 2108 L.sub.a3-208 L.sub.b209 L.sub.b209 2109 L.sub.a3-224 L.sub.b209 L.sub.b209 2110 L.sub.a3-258 L.sub.b209 L.sub.b209 2111 L.sub.a3-308 L.sub.b209 L.sub.b209 2112 L.sub.a3-321 L.sub.b209 L.sub.b209 2113 L.sub.a3-333 L.sub.b209 L.sub.b209 2114 L.sub.a3-339 L.sub.b209 L.sub.b209 2115 L.sub.a3-345 L.sub.b209 L.sub.b209 2116 L.sub.a3-382 L.sub.b209 L.sub.b209 2117 L.sub.a3-400 L.sub.b209 L.sub.b209 2118 L.sub.a3-418 L.sub.b209 L.sub.b209 2119 L.sub.a3-419 L.sub.b209 L.sub.b209 2120 L.sub.a3-440 L.sub.b209 L.sub.b209 2121 L.sub.a3-441 L.sub.b209 L.sub.b209 2122 L.sub.a3-446 L.sub.b209 L.sub.b209 2123 L.sub.a4-2 L.sub.b209 L.sub.b209 2124 L.sub.a4-4 L.sub.b209 L.sub.b209 2125 L.sub.a4-8 L.sub.b209 L.sub.b209 2126 L.sub.a4-10 L.sub.b209 L.sub.b209 2127 L.sub.a4-14 L.sub.b209 L.sub.b209 2128 L.sub.a4-16 L.sub.b209 L.sub.b209 2129 L.sub.a4-20 L.sub.b209 L.sub.b209 2130 L.sub.a4-22 L.sub.b209 L.sub.b209 2131 L.sub.a4-26 L.sub.b209 L.sub.b209 2132 L.sub.a4-28 L.sub.b209 L.sub.b209 2133 L.sub.a1-58 L.sub.b287 L.sub.b287 2134 L.sub.a1-88 L.sub.b287 L.sub.b287 2135 L.sub.a1-133 L.sub.b287 L.sub.b287 2136 L.sub.a1-146 L.sub.b287 L.sub.b287 2137 L.sub.a1-157 L.sub.b287 L.sub.b287 2138 L.sub.a1-158 L.sub.b287 L.sub.b287 2139 L.sub.a1-164 L.sub.b287 L.sub.b287 2140 L.sub.a1-170 L.sub.b287 L.sub.b287 2141 L.sub.a1-176 L.sub.b287 L.sub.b287 2142 L.sub.a1-208 L.sub.b287 L.sub.b287 2143 L.sub.a1-224 L.sub.b287 L.sub.b287 2144 L.sub.a1-258 L.sub.b287 L.sub.b287 2145 L.sub.a1-308 L.sub.b287 L.sub.b287 2146 L.sub.a1-321 L.sub.b287 L.sub.b287 2147 L.sub.a1-333 L.sub.b287 L.sub.b287 2148 L.sub.a1-339 L.sub.b287 L.sub.b287 2149 L.sub.a1-345 L.sub.b287 L.sub.b287 2150 L.sub.a1-382 L.sub.b287 L.sub.b287 2151 L.sub.a1-400 L.sub.b287 L.sub.b287 2152 L.sub.a1-418 L.sub.b287 L.sub.b287 2153 L.sub.a1-419 L.sub.b287 L.sub.b287 2154 L.sub.a1-440 L.sub.b287 L.sub.b287 2155 L.sub.a1-441 L.sub.b287 L.sub.b287 2156 L.sub.a1-446 L.sub.b287 L.sub.b287 2157 L.sub.a2-58 L.sub.b287 L.sub.b287 2158 L.sub.a2-88 L.sub.b287 L.sub.b287 2159 L.sub.a2-133 L.sub.b287 L.sub.b287 2160 L.sub.a2-146 L.sub.b287 L.sub.b287 2161 L.sub.a2-157 L.sub.b287 L.sub.b287 2162 L.sub.a2-158 L.sub.b287 L.sub.b287 2163 L.sub.a2-164 L.sub.b287 L.sub.b287 2164 L.sub.a2-170 L.sub.b287 L.sub.b287 2165 L.sub.a2-176 L.sub.b287 L.sub.b287 2166 L.sub.a2-208 L.sub.b287 L.sub.b287 2167 L.sub.a2-224 L.sub.b287 L.sub.b287 2168 L.sub.a2-258 L.sub.b287 L.sub.b287 2169 L.sub.a2-308 L.sub.b287 L.sub.b287 2170 L.sub.a2-321 L.sub.b287 L.sub.b287 2171 L.sub.a2-333 L.sub.b287 L.sub.b287 2172 L.sub.a2-339 L.sub.b287 L.sub.b287 2173 L.sub.a2-345 L.sub.b287 L.sub.b287 2174 L.sub.a2-382 L.sub.b287 L.sub.b287 2175 L.sub.a2-400 L.sub.b287 L.sub.b287 2176 L.sub.a2-418 L.sub.b287 L.sub.b287 2177 L.sub.a2-419 L.sub.b287 L.sub.b287 2178 L.sub.a2-440 L.sub.b287 L.sub.b287 2179 L.sub.a2-441 L.sub.b287 L.sub.b287 2180 L.sub.a2-446 L.sub.b287 L.sub.b287 2181 L.sub.a3-58 L.sub.b287 L.sub.b287 2182 L.sub.a3-88 L.sub.b287 L.sub.b287 2183 L.sub.a3-133 L.sub.b287 L.sub.b287 2184 L.sub.a3-146 L.sub.b287 L.sub.b287 2185 L.sub.a3-157 L.sub.b287 L.sub.b287 2186 L.sub.a3-158 L.sub.b287 L.sub.b287 2187 L.sub.a3-164 L.sub.b287 L.sub.b287 2188 L.sub.a3-170 L.sub.b287 L.sub.b287 2189 L.sub.a3-176 L.sub.b287 L.sub.b287 2190 L.sub.a3-208 L.sub.b287 L.sub.b287 2191 L.sub.a3-224 L.sub.b287 L.sub.b287 2192 L.sub.a3-258 L.sub.b287 L.sub.b287 2193 L.sub.a3-308 L.sub.b287 L.sub.b287 2194 L.sub.a3-321 L.sub.b287 L.sub.b287 2195 L.sub.a3-333 L.sub.b287 L.sub.b287 2196 L.sub.a3-339 L.sub.b287 L.sub.b287 2197 L.sub.a3-345 L.sub.b287 L.sub.b287 2198 L.sub.a3-382 L.sub.b287 L.sub.b287 2199 L.sub.a3-400 L.sub.b287 L.sub.b287 2200 L.sub.a3-418 L.sub.b287 L.sub.b287 2201 L.sub.a3-419 L.sub.b287 L.sub.b287 2202 L.sub.a3-440 L.sub.b287 L.sub.b287 2203 L.sub.a3-441 L.sub.b287 L.sub.b287 2204 L.sub.a3-446 L.sub.b287 L.sub.b287 2205 L.sub.a4-2 L.sub.b287 L.sub.b287 2206 L.sub.a4-4 L.sub.b287 L.sub.b287 2207 L.sub.a4-8 L.sub.b287 L.sub.b287 2208 L.sub.a4-10 L.sub.b287 L.sub.b287 2209 L.sub.a4-14 L.sub.b287 L.sub.b287 2210 L.sub.a4-16 L.sub.b287 L.sub.b287 2211 L.sub.a4-20 L.sub.b287 L.sub.b287 2212 L.sub.a4-22 L.sub.b287 L.sub.b287 2213 L.sub.a4-26 L.sub.b287 L.sub.b287 2214 L.sub.a4-28 L.sub.b287 L.sub.b287 2215 L.sub.a1-58 L.sub.b289 L.sub.b289 2216 L.sub.a1-88 L.sub.b289 L.sub.b289 2217 L.sub.a1-133 L.sub.b289 L.sub.b289 2218 L.sub.a1-146 L.sub.b289 L.sub.b289 2219 L.sub.a1-157 L.sub.b289 L.sub.b289 2220 L.sub.a1-158 L.sub.b289 L.sub.b289 2221 L.sub.a1-164 L.sub.b289 L.sub.b289 2222 L.sub.a1-170 L.sub.b289 L.sub.b289 2223 L.sub.a1-176 L.sub.b289 L.sub.b289 2224 L.sub.a1-208 L.sub.b289 L.sub.b289 2225 L.sub.a1-224 L.sub.b289 L.sub.b289 2226 L.sub.a1-258 L.sub.b289 L.sub.b289 2227 L.sub.a1-308 L.sub.b289 L.sub.b289 2228 L.sub.a1-321 L.sub.b289 L.sub.b289 2229 L.sub.a1-333 L.sub.b289 L.sub.b289 2230 L.sub.a1-339 L.sub.b289 L.sub.b289 2231 L.sub.a1-345 L.sub.b289 L.sub.b289 2232 L.sub.a1-382 L.sub.b289 L.sub.b289 2233 L.sub.a1-400 L.sub.b289 L.sub.b289 2234 L.sub.a1-418 L.sub.b289 L.sub.b289 2235 L.sub.a1-419 L.sub.b289 L.sub.b289 2236 L.sub.a1-440 L.sub.b289 L.sub.b289 2237 L.sub.a1-441 L.sub.b289 L.sub.b289 2238 L.sub.a1-446 L.sub.b289 L.sub.b289 2239 L.sub.a2-58 L.sub.b289 L.sub.b289 2240 L.sub.a2-88 L.sub.b289 L.sub.b289 2241 L.sub.a2-133 L.sub.b289 L.sub.b289 2242 L.sub.a2-146 L.sub.b289 L.sub.b289 2243 L.sub.a2-157 L.sub.b289 L.sub.b289 2244 L.sub.a2-158 L.sub.b289 L.sub.b289 2245 L.sub.a2-164 L.sub.b289 L.sub.b289 2246 L.sub.a2-170 L.sub.b289 L.sub.b289 2247 L.sub.a2-176 L.sub.b289 L.sub.b289 2248 L.sub.a2-208 L.sub.b289 L.sub.b289 2249 L.sub.a2-224 L.sub.b289 L.sub.b289 2250 L.sub.a2-258 L.sub.b289 L.sub.b289 2251 L.sub.a2-308 L.sub.b289 L.sub.b289 2252 L.sub.a2-321 L.sub.b289 L.sub.b289 2253 L.sub.a2-333 L.sub.b289 L.sub.b289 2254 L.sub.a2-339 L.sub.b289 L.sub.b289 2255 L.sub.a2-345 L.sub.b289 L.sub.b289 2256 L.sub.a2-382 L.sub.b289 L.sub.b289 2257 L.sub.a2-400 L.sub.b289 L.sub.b289 2258 L.sub.a2-418 L.sub.b289 L.sub.b289 2259 L.sub.a2-419 L.sub.b289 L.sub.b289 2260 L.sub.a2-440 L.sub.b289 L.sub.b289 2261 L.sub.a2-441 L.sub.b289 L.sub.b289 2262 L.sub.a2-446 L.sub.b289 L.sub.b289 2263 L.sub.a3-58 L.sub.b289 L.sub.b289 2264 L.sub.a3-88 L.sub.b289 L.sub.b289 2265 L.sub.a3-133 L.sub.b289 L.sub.b289 2266 L.sub.a3-146 L.sub.b289 L.sub.b289 2267 L.sub.a3-157 L.sub.b289 L.sub.b289 2268 L.sub.a3-158 L.sub.b289 L.sub.b289 2269 L.sub.a3-164 L.sub.b289 L.sub.b289 2270 L.sub.a3-170 L.sub.b289 L.sub.b289 2271 L.sub.a3-176 L.sub.b289 L.sub.b289 2272 L.sub.a3-208 L.sub.b289 L.sub.b289 2273 L.sub.a3-224 L.sub.b289 L.sub.b289 2274 L.sub.a3-258 L.sub.b289 L.sub.b289 2275 L.sub.a3-308 L.sub.b289 L.sub.b289 2276 L.sub.a3-321 L.sub.b289 L.sub.b289 2277 L.sub.a3-333 L.sub.b289 L.sub.b289 2278 L.sub.a3-339 L.sub.b289 L.sub.b289 2279 L.sub.a3-345 L.sub.b289 L.sub.b289 2280 L.sub.a3-382 L.sub.b289 L.sub.b289 2281 L.sub.a3-400 L.sub.b289 L.sub.b289 2282 L.sub.a3-418 L.sub.b289 L.sub.b289 2283 L.sub.a3-419 L.sub.b289 L.sub.b289 2284 L.sub.a3-440 L.sub.b289 L.sub.b289 2285 L.sub.a3-441 L.sub.b289 L.sub.b289 2286 L.sub.a3-446 L.sub.b289 L.sub.b289 2287 L.sub.a4-2 L.sub.b289 L.sub.b289 2288 L.sub.a4-4 L.sub.b289 L.sub.b289 2289 L.sub.a4-8 L.sub.b289 L.sub.b289 2290 L.sub.a4-10 L.sub.b289 L.sub.b289 2291 L.sub.a4-14 L.sub.b289 L.sub.b289 2292 L.sub.a4-16 L.sub.b289 L.sub.b289 2293 L.sub.a4-20 L.sub.b289 L.sub.b289 2294 L.sub.a4-22 L.sub.b289 L.sub.b289 2295 L.sub.a4-26 L.sub.b289 L.sub.b289 2296 L.sub.a4-28 L.sub.b289 L.sub.b289 2297 L.sub.a2-146 L.sub.b1 L.sub.b3 2298 L.sub.a2-146 L.sub.b1 L.sub.b81 2299 L.sub.a2-146 L.sub.b3 L.sub.b12 2300 L.sub.a2-146 L.sub.b3 L.sub.b81 2301 L.sub.a2-158 L.sub.b1 L.sub.b3 2302 L.sub.a2-158 L.sub.b1 L.sub.b3 2303 L.sub.a2-158 L.sub.b3 L.sub.b12 2304 L.sub.a2-158 L.sub.b3 L.sub.b12 2305 L.sub.a2-164 L.sub.b1 L.sub.b3 2306 L.sub.a2-164 L.sub.b1 L.sub.b3 2307 L.sub.a2-164 L.sub.b3 L.sub.b12 2308 L.sub.a2-164 L.sub.b3 L.sub.b12 2309 L.sub.a2-176 L.sub.b1 L.sub.b3 2310 L.sub.a2-176 L.sub.b1 L.sub.b3 2311 L.sub.a2-176 L.sub.b3 L.sub.b12 2312 L.sub.a2-176 L.sub.b3 L.sub.b12 2313 L.sub.a2-321 L.sub.b1 L.sub.b3 2314 L.sub.a2-321 L.sub.b1 L.sub.b3 2315 L.sub.a2-321 L.sub.b3 L.sub.b12 2316 L.sub.a2-321 L.sub.b3 L.sub.b12 2317 L.sub.a2-345 L.sub.b1 L.sub.b3 2318 L.sub.a2-345 L.sub.b1 L.sub.b3 2319 L.sub.a2-345 L.sub.b3 L.sub.b12 2320 L.sub.a2-345 L.sub.b3 L.sub.b12 2321 L.sub.a3-146 L.sub.b1 L.sub.b3 2322 L.sub.a3-146 L.sub.b1 L.sub.b3 2323 L.sub.a3-146 L.sub.b3 L.sub.b12 2324 L.sub.a3-146 L.sub.b3 L.sub.b12 2325 L.sub.a3-158 L.sub.b1 L.sub.b3 2326 L.sub.a3-158 L.sub.b1 L.sub.b3 2327 L.sub.a3-158 L.sub.b3 L.sub.b12 2328 L.sub.a3-158 L.sub.b3 L.sub.b12 2329 L.sub.a3-164 L.sub.b1 L.sub.b3 2330 L.sub.a3-164 L.sub.b1 L.sub.b3 2331 L.sub.a3-164 L.sub.b3 L.sub.b12 2332 L.sub.a3-164 L.sub.b3 L.sub.b12 2333 L.sub.a3-176 L.sub.b1 L.sub.b3 2334 L.sub.a3-176 L.sub.b1 L.sub.b3 2335 L.sub.a3-176 L.sub.b3 L.sub.b12 2336 L.sub.a3-176 L.sub.b3 L.sub.b12 2337 L.sub.a3-321 L.sub.b1 L.sub.b3 2338 L.sub.a3-321 L.sub.b1 L.sub.b3 2339 L.sub.a3-321 L.sub.b3 L.sub.b12 2340 L.sub.a3-321 L.sub.b3 L.sub.b12 2341 L.sub.a3-345 L.sub.b1 L.sub.b3 2342 L.sub.a3-345 L.sub.b1 L.sub.b3 2343 L.sub.a3-345 L.sub.b3 L.sub.b12 2344 L.sub.a3-345 L.sub.b3 L.sub.b12; Metal Complex 2345 to Metal Complex 2384 each have a structure of Ir(L.sub.a).sub.2L.sub.b, wherein the two L.sub.a are the same or different, and the two L.sub.a and L.sub.b respectively correspond to the structures listed in the following table: TABLE-US-00006 Metal Metal Complex L.sub.a L.sub.a L.sub.b Complex L.sub.a L.sub.a L.sub.b 2345 L.sub.a1-146 L.sub.a1-146 L.sub.b3 2346 L.sub.a1-158 L.sub.a1-158 L.sub.b3 2347 L.sub.a1-164 L.sub.a1-164 L.sub.b3 2348 L.sub.a1-176 L.sub.a1-176 L.sub.b3 2349 L.sub.a1-321 L.sub.a1-321 L.sub.b3 2350 L.sub.a1-345 L.sub.a1-345 L.sub.b3 2351 L.sub.a1-146 L.sub.a1-146 L.sub.b81 2352 L.sub.a1-158 L.sub.a1-158 L.sub.b81 2353 L.sub.a1-164 L.sub.a1-164 L.sub.b81 2354 L.sub.a1-176 L.sub.a1-176 L.sub.b81 2355 L.sub.a1-321 L.sub.a1-321 L.sub.b81 2356 L.sub.a1-345 L.sub.a1-345 L.sub.b81 2357 L.sub.a2-146 L.sub.a2-146 L.sub.b3 2358 L.sub.a2-158 L.sub.a2-158 L.sub.b3 2359 L.sub.a2-164 L.sub.a2-164 L.sub.b3 2360 L.sub.a2-176 L.sub.a2-176 L.sub.b3 2361 L.sub.a2-321 L.sub.a2-321 L.sub.b3 2362 L.sub.a2-345 L.sub.a2-345 L.sub.b3 2363 L.sub.a2-146 L.sub.a2-146 L.sub.b81 2364 L.sub.a2-158 L.sub.a2-158 L.sub.b81 2365 L.sub.a2-164 L.sub.a2-164 L.sub.b81 2366 L.sub.a2-176 L.sub.a2-176 L.sub.b81 2367 L.sub.a2-321 L.sub.a2-321 L.sub.b81 2368 L.sub.a2-345 L.sub.a2-345 L.sub.b81 2369 L.sub.a3-146 L.sub.a3-146 L.sub.b3 2370 L.sub.a3-158 L.sub.a3-158 L.sub.b3 2371 L.sub.a3-164 L.sub.a3-164 L.sub.b3 2372 L.sub.a3-176 L.sub.a3-176 L.sub.b3 2373 L.sub.a3-321 L.sub.a3-321 L.sub.b3 2374 L.sub.a3-345 L.sub.a3-345 L.sub.b3 2375 L.sub.a3-146 L.sub.a3-146 L.sub.b81 2376 L.sub.a3-158 L.sub.a3-158 L.sub.b81 2377 L.sub.a3-164 L.sub.a3-164 L.sub.b81 2378 L.sub.a3-176 L.sub.a3-176 L.sub.b81 2379 L.sub.a3-321 L.sub.a3-321 L.sub.b81 2380 L.sub.a3-345 L.sub.a3-345 L.sub.b81 2381 L.sub.a2-164 L.sub.a2-176 L.sub.b3 2382 L.sub.a2-176 L.sub.a3-345 L.sub.b3 2383 L.sub.a2-164 L.sub.a2-176 L.sub.b81 2384 L.sub.a2-164 L.sub.a2-176 L.sub.b81; Metal Complex 2385 to Metal Complex 2424 each have a structure of Ir(L.sub.a).sub.2L.sub.c, wherein the two L.sub.a are the same or different, and the two L.sub.a and L.sub.c respectively correspond to the structures listed in the following table: TABLE-US-00007 Metal Metal Complex L.sub.a L.sub.a L.sub.c Complex L.sub.a L.sub.a L.sub.c 2385 L.sub.a1-146 L.sub.a1-146 L.sub.c1 2386 L.sub.a1-158 L.sub.a1-158 L.sub.c1 2387 L.sub.a1-164 L.sub.a1-164 L.sub.c1 2388 L.sub.a1-176 L.sub.a1-176 L.sub.c1 2389 L.sub.a1-321 L.sub.a1-321 L.sub.c1 2390 L.sub.a1-345 L.sub.a1-345 L.sub.c1 2391 L.sub.a1-146 L.sub.a1-146 L.sub.c31 2392 L.sub.a1-158 L.sub.a1-158 L.sub.c31 2393 L.sub.a1-164 L.sub.a1-164 L.sub.c31 2394 L.sub.a1-176 L.sub.a1-176 L.sub.c31 2395 L.sub.a1-321 L.sub.a1-321 L.sub.c31 2396 L.sub.a1-345 L.sub.a1-345 L.sub.c31 2397 L.sub.a2-146 L.sub.a2-146 L.sub.c1 2398 L.sub.a2-158 L.sub.a2-158 L.sub.c1 2399 L.sub.a2-164 L.sub.a2-164 L.sub.c1 2400 L.sub.a2-176 L.sub.a2-176 L.sub.c1 2401 L.sub.a2-321 L.sub.a2-321 L.sub.c1 2402 L.sub.a2-345 L.sub.a2-345 L.sub.c1 2403 L.sub.a2-146 L.sub.a2-146 L.sub.c31 2404 L.sub.a2-158 L.sub.a2-158 L.sub.c31 2405 L.sub.a2-164 L.sub.a2-164 L.sub.c31 2406 L.sub.a2-176 L.sub.a2-176 L.sub.c31 2407 L.sub.a2-321 L.sub.a2-321 L.sub.c31 2408 L.sub.a2-345 L.sub.a2-345 L.sub.c31 2409 L.sub.a3-146 L.sub.a3-146 L.sub.c1 2410 L.sub.a3-158 L.sub.a3-158 L.sub.c1 2411 L.sub.a3-164 L.sub.a3-164 L.sub.c1 2412 L.sub.a3-176 L.sub.a3-176 L.sub.c1 2413 L.sub.a3-321 L.sub.a3-321 L.sub.c1 2414 L.sub.a3-345 L.sub.a3-345 L.sub.c1 2415 L.sub.a3-146 L.sub.a3-146 L.sub.c31 2416 L.sub.a3-158 L.sub.a3-158 L.sub.c31 2417 L.sub.a3-164 L.sub.a3-164 L.sub.c31 2418 L.sub.a3-176 L.sub.a3-176 L.sub.c31 2419 L.sub.a3-321 L.sub.a3-321 L.sub.c31 2420 L.sub.a3-345 L.sub.a3-345 L.sub.c31 2421 L.sub.a2-164 L.sub.a2-176 L.sub.c1 2422 L.sub.a2-176 L.sub.a3-345 L.sub.c1 2423 L.sub.a2-164 L.sub.a2-176 L.sub.c31 2424 L.sub.a2-164 L.sub.a2-176 L.sub.c31; Metal Complex 2425 to Metal Complex 2440 each have a structure of Ir(L.sub.a)(L.sub.b)(L.sub.c), wherein L.sub.a, L.sub.b and L.sub.c respectively correspond to the structures listed in the following table: TABLE-US-00008 Metal Metal Complex L.sub.a L.sub.b L.sub.c Complex L.sub.a L.sub.b L.sub.c 2425 L.sub.a1-164 L.sub.b3 L.sub.c1 2426 L.sub.a1-176 L.sub.b3 L.sub.c1 2427 L.sub.a1-321 L.sub.b3 L.sub.c1 2428 L.sub.a1-345 L.sub.b3 L.sub.c1 2429 L.sub.a1-164 L.sub.b81 L.sub.c1 2430 L.sub.a1-176 L.sub.b81 L.sub.c1 2431 L.sub.a1-321 L.sub.b81 L.sub.c1 2432 L.sub.a1-345 L.sub.b81 L.sub.c1 2433 L.sub.a1-164 L.sub.b3 L.sub.c31 2434 L.sub.a1-176 L.sub.a1-176 L.sub.c31 2435 L.sub.a1-321 L.sub.b3 L.sub.c31 2436 L.sub.a1-345 L.sub.a1-345 L.sub.c31 2437 L.sub.a2-146 L.sub.b81 L.sub.c31 2438 L.sub.a2-158 L.sub.a2-158 L.sub.c31 2439 L.sub.a2-164 L.sub.b81 L.sub.c31 2440 L.sub.a2-176 L.sub.a2-176 L.sub.c31; Metal Complex 2441 to Metal Complex 2454 each have a structure of Ir(L.sub.a).sub.3, wherein the three L.sub.a are the same or different, and the three L.sub.a respectively correspond to the structures listed in the following table: TABLE-US-00009 Metal Metal Complex L.sub.a L.sub.a L.sub.a Complex L.sub.a L.sub.a L.sub.a 2441 L.sub.a1-164 L.sub.a1-164 L.sub.a1-164 2442 L.sub.a1-176 L.sub.a1-176 L.sub.a1-176 2443 L.sub.a1-321 L.sub.a1-321 L.sub.a1-321 2444 L.sub.a1-345 L.sub.a1-345 L.sub.a1-345 2445 L.sub.a2-164 L.sub.a2-164 L.sub.a2-164 2446 L.sub.a2-176 L.sub.a2-176 L.sub.a2-176 2447 L.sub.a2-321 L.sub.a2-321 L.sub.a2-321 2448 L.sub.a2-345 L.sub.a2-345 L.sub.a2-345 2449 L.sub.a3-164 L.sub.a3-164 L.sub.a3-164 2450 L.sub.a3-176 L.sub.a3-176 L.sub.a3-176 2451 L.sub.a3-321 L.sub.a3-321 L.sub.a3-321 2452 L.sub.a3-345 L.sub.a3-345 L.sub.a3-345 2453 L.sub.a1-164 L.sub.a1-164 L.sub.a2-164 2454 L.sub.a1-176 L.sub.a1-176 L.sub.a2-176 2455 L.sub.a1-321 L.sub.a1-321 L.sub.a3-321 2456 L.sub.a1-345 L.sub.a1-345 L.sub.a3-321 2453 L.sub.a1-164 L.sub.a2-321 L.sub.a3-321 2454 L.sub.a1-176 L.sub.a3-345 L.sub.a3-321 2455 L.sub.a1-345 L.sub.a2-321 L.sub.a3-176 2456 L.sub.a2-321 L.sub.a2-345 L.sub.a3-345 2453 L.sub.a2-321 L.sub.a3-164 L.sub.a3-321 2454 L.sub.a2-345 L.sub.a3-176 L.sub.a3-345.
21. An electroluminescent device, comprising: an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises the metal complex of claim 1.
22. The electroluminescent device of claim 21, wherein the organic layer comprising the metal complex is a light-emitting layer.
23. The electroluminescent device of claim 22, wherein the electroluminescent device emits green light or white light.
24. The electroluminescent device of claim 22, wherein the light-emitting layer comprises a first host compound; preferably, the light-emitting layer further comprises a second host compound; more preferably, the first host compound and/or the second host compound comprise at least one chemical group selected from the group consisting of benzene, pyridine, pyrimidine, triazine, carbazole, azacarbazole, indolocarbazole, dibenzothiophene, aza-dibenzothiophene, dibenzofuran, azadibenzofuran, dibenzoselenophene, triphenylene, azatriphenylene, fluorene, silafluorene, naphthalene, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene, azaphenanthrene and combinations thereof.
25. The electroluminescent device of claim 24, wherein the first host compound has a structure represented by Formula 4: ##STR00595## wherein E.sub.1 to E.sub.6 are, at each occurrence identically or differently, selected from C, CR.sub.e or N, at least two of E.sub.1 to E.sub.6 are N, and at least one of E.sub.1 to E.sub.6 is C and joined to Formula A; ##STR00596## wherein Q is, at each occurrence identically or differently, selected from the group consisting of O, S, Se, N, NR′″, CR′″R′″, SiR′″R′″, GeR′″R′″ and R′″C═CR′″; when two R′″ are present at the same time, the two R′″ may be the same or different; p is 0 or 1; r is 0 or 1; when Q is selected from N, p is 0 and r is 1; when Q is selected from the group consisting of O, S, Se, NR′″, CR′″R′″, SiR′″R′″, GeR′″R′″ and R′″C═CR′″, p is 1 and r is 0; L is, at each occurrence identically or differently, selected from a single bond, substituted or unsubstituted alkylene having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkylene having 3 to 20 carbon atoms, substituted or unsubstituted arylene having 6 to 20 carbon atoms, substituted or unsubstituted heteroarylene having 3 to 20 carbon atoms or a combination thereof; Q.sub.1 to Q.sub.8 are, at each occurrence identically or differently, selected from C, CR.sub.q or N; R.sub.e, R′″ and R.sub.q are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof; “*k” represents a position where Formula A is joined to Formula 4; and adjacent substituents R.sub.e, R′″, R.sub.q can be optionally joined to form a ring; preferably, the first host compound is selected from the group consisting of the following ##STR00597## ##STR00598## ##STR00599## ##STR00600## ##STR00601## ##STR00602## ##STR00603## ##STR00604## ##STR00605## ##STR00606## ##STR00607## ##STR00608## ##STR00609## ##STR00610## ##STR00611## ##STR00612## ##STR00613## ##STR00614## ##STR00615## ##STR00616## ##STR00617## ##STR00618## ##STR00619## ##STR00620## ##STR00621## ##STR00622## ##STR00623## ##STR00624## ##STR00625## ##STR00626## ##STR00627## ##STR00628## ##STR00629## ##STR00630## ##STR00631## ##STR00632## ##STR00633## ##STR00634## ##STR00635## ##STR00636## ##STR00637## ##STR00638## ##STR00639##
26. The electroluminescent device of claim 24, wherein the second host compound has a structure represented by Formula 5: ##STR00640## wherein L.sub.x is, at each occurrence identically or differently, selected from a single bond, substituted or unsubstituted alkylene having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkylene having 3 to 20 carbon atoms, substituted or unsubstituted arylene having 6 to 20 carbon atoms, substituted or unsubstituted heteroarylene having 3 to 20 carbon atoms or a combination thereof; V is, at each occurrence identically or differently, selected from C, CR.sub.v or N, and at least one of V is C and joined to L.sub.x; U is, at each occurrence identically or differently, selected from C, CR.sub.u or N, and at least one of U is C and joined to L.sub.x; R.sub.v and R.sub.u are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof; Ar.sub.6 is, at each occurrence identically or differently, selected from substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms or a combination thereof; and adjacent substituents R, and R.sub.u can be optionally joined to form a ring; preferably, the second host compound has a structure represented by one of Formula 5-a to Formula 5-j: ##STR00641## ##STR00642## more preferably, the second host compound is selected from the group consisting of the following: ##STR00643## ##STR00644## ##STR00645## ##STR00646## ##STR00647## ##STR00648## ##STR00649## ##STR00650## ##STR00651## ##STR00652## ##STR00653## ##STR00654## ##STR00655## ##STR00656## ##STR00657## ##STR00658## ##STR00659## ##STR00660## ##STR00661## ##STR00662## ##STR00663## ##STR00664## ##STR00665## ##STR00666## ##STR00667## ##STR00668## ##STR00669## ##STR00670## ##STR00671## ##STR00672## ##STR00673## ##STR00674## ##STR00675## ##STR00676## ##STR00677## ##STR00678## ##STR00679## ##STR00680## ##STR00681## ##STR00682## ##STR00683## ##STR00684## ##STR00685## ##STR00686## ##STR00687## ##STR00688## ##STR00689## ##STR00690## ##STR00691## ##STR00692## ##STR00693## ##STR00694## ##STR00695## ##STR00696## ##STR00697## ##STR00698## ##STR00699## ##STR00700## ##STR00701## ##STR00702## ##STR00703## ##STR00704##
27. The electroluminescent device of claim 24, wherein the metal complex is doped in the first host compound and the second host compound, and a weight of the metal complex accounts for 1% to 30% of a total weight of the light-emitting layer; preferably, the weight of the metal complex accounts for 3% to 13% of the total weight of the light-emitting layer.
28. A compound combination, comprising the metal complex of claim 1.
Description
BRIEF DESCRIPTION OF DRAWINGS
[0033]
[0034]
DETAILED DESCRIPTION
[0035] OLEDs can be fabricated on various types of substrates such as glass, plastic, and metal foil.
[0036] More examples for each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference herein in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference herein in its entirety. Examples of host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which is incorporated by reference herein in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference herein in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference herein in their entireties, disclose examples of cathodes including composite cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, electrically-conductive, sputter-deposited ITO layer. The theory and use of blocking layers are described in more detail in U.S. Pat. No. 6,097,147 and U.S. Patent Application Publication No. 2003/0230980, which are incorporated by reference herein in their entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference herein in its entirety. A description of protective layers may be found in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference herein in its entirety.
[0037] The layered structure described above is provided by way of non-limiting examples. Functional OLEDs may be achieved by combining the various layers described in different ways, or layers may be omitted entirely. It may also include other layers not specifically described. Within each layer, a single material or a mixture of multiple materials can be used to achieve optimum performance. Any functional layer may include several sublayers. For example, the emissive layer may have two layers of different emitting materials to achieve desired emission spectrum.
[0038] In one embodiment, an OLED may be described as having an “organic layer” disposed between a cathode and an anode. This organic layer may include a single layer or multiple layers.
[0039] An OLED can be encapsulated by a barrier layer.
[0040] Devices fabricated in accordance with embodiments of the present disclosure can be incorporated into a wide variety of consumer products that have one or more of the electronic component modules (or units) incorporated therein. Some examples of such consumer products include flat panel displays, monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, smart phones, tablets, phablets, wearable devices, smart watches, laptop computers, digital cameras, camcorders, viewfinders, micro-displays, 3-D displays, vehicles displays, and vehicle tail lights.
[0041] The materials and structures described herein may be used in other organic electronic devices listed above.
[0042] As used herein, “top” means furthest away from the substrate, while “bottom” means closest to the substrate. Where a first layer is described as “disposed over” a second layer, the first layer is disposed further away from the substrate. There may be other layers between the first and second layers, unless it is specified that the first layer is “in contact with” the second layer. For example, a cathode may be described as “disposed over” an anode, even though there are various organic layers in between.
[0043] As used herein, “solution processible” means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium, either in solution or suspension form.
[0044] A ligand may be referred to as “photoactive” when it is believed that the ligand directly contributes to the photoactive properties of an emissive material. A ligand may be referred to as “ancillary” when it is believed that the ligand does not contribute to the photoactive properties of an emissive material, although an ancillary ligand may alter the properties of a photoactive ligand.
[0045] It is believed that the internal quantum efficiency (IQE) of fluorescent OLEDs can exceed the 25% spin statistics limit through delayed fluorescence. As used herein, there are two types of delayed fluorescence, i.e. P-type delayed fluorescence and E-type delayed fluorescence. P-type delayed fluorescence is generated from triplet-triplet annihilation (TTA).
[0046] On the other hand, E-type delayed fluorescence does not rely on the collision of two triplets, but rather on the transition between the triplet states and the singlet excited states. Compounds that are capable of generating E-type delayed fluorescence are required to have very small singlet-triplet gaps to convert between energy states. Thermal energy can activate the transition from the triplet state back to the singlet state. This type of delayed fluorescence is also known as thermally activated delayed fluorescence (TADF). A distinctive feature of TADF is that the delayed component increases as temperature rises. If the reverse intersystem crossing (RISC) rate is fast enough to minimize the non-radiative decay from the triplet state, the fraction of back populated singlet excited states can potentially reach 75%. The total singlet fraction can be 100%, far exceeding 25% of the spin statistics limit for electrically generated excitons.
[0047] E-type delayed fluorescence characteristics can be found in an exciplex system or in a single compound. Without being bound by theory, it is believed that E-type delayed fluorescence requires the luminescent material to have a small singlet-triplet energy gap (Δ.sub.ES-T). Organic, non-metal containing, donor-acceptor luminescent materials may be able to achieve this. The emission in these materials is generally characterized as a donor-acceptor charge-transfer (CT) type emission. The spatial separation of the HOMO and LUMO in these donor-acceptor type compounds generally results in small Δ.sub.ES-T. These states may involve CT states. Generally, donor-acceptor luminescent materials are constructed by connecting an electron donor moiety such as amino- or carbazole-derivatives and an electron acceptor moiety such as N-containing six-membered aromatic rings.
Definition of Terms of Substituents
[0048] Halogen or halide—as used herein includes fluorine, chlorine, bromine, and iodine.
[0049] Alkyl—as used herein includes both straight and branched chain alkyl groups. Alkyl may be alkyl having 1 to 20 carbon atoms, preferably alkyl having 1 to 12 carbon atoms, and more preferably alkyl having 1 to 6 carbon atoms. Examples of alkyl groups include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an s-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, a neopentyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 1-pentylhexyl group, a 1-butylpentyl group, a 1-heptyloctyl group, and a 3-methylpentyl group. Of the above, preferred are a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an s-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, a neopentyl group, and an n-hexyl group. Additionally, the alkyl group may be optionally substituted.
[0050] Cycloalkyl—as used herein includes cyclic alkyl groups. The cycloalkyl groups may be those having 3 to 20 ring carbon atoms, preferably those having 4 to 10 carbon atoms. Examples of cycloalkyl include cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4,4-dimethylcylcohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl, and the like. Of the above, preferred are cyclopentyl, cyclohexyl, 4-methylcyclohexyl, and 4,4-dimethylcylcohexyl. Additionally, the cycloalkyl group may be optionally substituted.
[0051] Heteroalkyl—as used herein, includes a group formed by replacing one or more carbons in an alkyl chain with a hetero-atom(s) selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, a phosphorus atom, a silicon atom, a germanium atom, and a boron atom. Heteroalkyl may be those having 1 to 20 carbon atoms, preferably those having 1 to 10 carbon atoms, and more preferably those having 1 to 6 carbon atoms. Examples of heteroalkyl include methoxymethyl, ethoxymethyl, ethoxyethyl, methylthiomethyl, ethylthiomethyl, ethylthioethyl, methoxymethoxymethyl, ethoxymethoxymethyl, ethoxyethoxyethyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, mercaptomethyl, mercaptoethyl, mercaptopropyl, aminomethyl, aminoethyl, aminopropyl, dimethylaminomethyl, trimethylgermanylmethyl, trimethylgermanylethyl, trimethylgermanylisopropyl, dimethylethylgermanylmethyl, dimethylisopropylgermanylmethyl, tert-butylmethylgermanylmethyl, triethylgermanylmethyl, triethylgermanylethyl, triisopropylgermanylmethyl, triisopropylgermanylethyl, trimethylsilylmethyl, trimethylsilylethyl, trimethylsilylisopropyl, triisopropylsilylmethyl, and triisopropylsilylethyl. Additionally, the heteroalkyl group may be optionally substituted.
[0052] Alkenyl—as used herein includes straight chain, branched chain, and cyclic alkene groups. Alkenyl may be those having 2 to 20 carbon atoms, preferably those having 2 to 10 carbon atoms. Examples of alkenyl include vinyl, 1-propenyl group, 1-butenyl, 2-butenyl, 3-butenyl, 1,3-butandienyl, 1-methylvinyl, styryl, 2,2-diphenylvinyl, 1,2-diphenylvinyl, 1-methylallyl, 1,1-dimethylallyl, 2-methylallyl, 1-phenylallyl, 2-phenylallyl, 3-phenylallyl, 3,3-diphenylallyl, 1,2-dimethylallyl, 1-phenyl-1-butenyl, 3-phenyl-1-butenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cycloheptenyl, cycloheptatrienyl, cyclooctenyl, cyclooctatetraenyl, and norbornenyl. Additionally, the alkenyl group may be optionally substituted.
[0053] Alkynyl—as used herein includes straight chain alkynyl groups. Alkynyl may be those having 2 to 20 carbon atoms, preferably those having 2 to 10 carbon atoms. Examples of alkynyl groups include ethynyl, propynyl, propargyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3,3-dimethyl-1-butynyl, 3-ethyl-3-methyl-1-pentynyl, 3,3-diisopropyl-1-pentynyl, phenylethynyl, phenylpropynyl, etc. Of the above, preferred are ethynyl, propynyl, propargyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, and phenylethynyl. Additionally, the alkynyl group may be optionally substituted.
[0054] Aryl or an aromatic group or an aromatic ring—as used herein includes non-condensed and condensed systems. Aryl may be those having 6 to 30 carbon atoms, preferably those having 6 to 20 carbon atoms, and more preferably those having 6 to 12 carbon atoms. Examples of aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene, and naphthalene. Examples of non-condensed aryl groups include phenyl, biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl, o-tolyl, m-tolyl, p-tolyl, p-(2-phenylpropyl)phenyl, 4′-methylbiphenylyl, 4″-t-butyl-p-terphenyl-4-yl, o-cumenyl, m-cumenyl, p-cumenyl, 2,3-xylyl, 3,4-xylyl, 2,5-xylyl, mesityl, and m-quarterphenyl. Additionally, the aryl group may be optionally substituted.
[0055] Heterocyclic groups or heterocycle—as used herein include non-aromatic cyclic groups. Non-aromatic heterocyclic groups includes saturated heterocyclic groups having 3 to 20 ring atoms and unsaturated non-aromatic heterocyclic groups having 3 to 20 ring atoms, where at least one ring atom is selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, a silicon atom, a phosphorus atom, a germanium atom, and a boron atom. Preferred non-aromatic heterocyclic groups are those having 3 to 7 ring atoms, each of which includes at least one hetero-atom such as nitrogen, oxygen, silicon, or sulfur. Examples of non-aromatic heterocyclic groups include oxiranyl, oxetanyl, tetrahydrofuranyl, tetrahydropyranyl, dioxolanyl, dioxanyl, aziridinyl, dihydropyrrolyl, tetrahydropyrrolyl, piperidinyl, oxazolidinyl, morpholinyl, piperazinyl, oxepinyl, thiepinyl, azepinyl, and tetrahydrosilolyl. Additionally, the heterocyclic group may be optionally substituted.
[0056] Heteroaryl or a heteroaromatic ring—as used herein, includes non-condensed and condensed hetero-aromatic groups having 1 to 5 hetero-atoms, where at least one hetero-atom is selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, a silicon atom, a phosphorus atom, a germanium atom, and a boron atom. A hetero-aromatic group is also referred to as heteroaryl. Heteroaryl may be those having 3 to 30 carbon atoms, preferably those having 3 to 20 carbon atoms, and more preferably those having 3 to 12 carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridoindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine, and aza-analogs thereof. Additionally, the heteroaryl group may be optionally substituted.
[0057] Alkoxy—as used herein, is represented by —O-alkyl, —O-cycloalkyl, —O-heteroalkyl, or —O-heterocyclic group. Examples and preferred examples of alkyl, cycloalkyl, heteroalkyl, and heterocyclic groups are the same as those described above. Alkoxy groups may be those having 1 to 20 carbon atoms, preferably those having 1 to 6 carbon atoms. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, tetrahydrofuranyloxy, tetrahydropyranyloxy, methoxypropyloxy, ethoxyethyloxy, methoxymethyloxy, and ethoxymethyloxy. Additionally, the alkoxy group may be optionally substituted.
[0058] Aryloxy—as used herein, is represented by —O-aryl or —O-heteroaryl. Examples and preferred examples of aryl and heteroaryl are the same as those described above. Aryloxy groups may be those having 6 to 30 carbon atoms, preferably those having 6 to 20 carbon atoms. Examples of aryloxy groups include phenoxy and biphenyloxy. Additionally, the aryloxy group may be optionally substituted.
[0059] Arylalkyl—as used herein, contemplates alkyl substituted with an aryl group. Arylalkyl may be those having 7 to 30 carbon atoms, preferably those having 7 to 20 carbon atoms, and more preferably those having 7 to 13 carbon atoms. Examples of arylalkyl groups include benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, 2-phenylisopropyl, phenyl-t-butyl, alpha-naphthylmethyl, 1-alpha-naphthylethyl, 2-alpha-naphthylethyl, 1-alpha-naphthylisopropyl, 2-alpha-naphthylisopropyl, beta-naphthylmethyl, 1-beta-naphthylethyl, 2-beta-naphthylethyl, 1-beta-naphthylisopropyl, 2-beta-naphthylisopropyl, p-methylbenzyl, m-methylbenzyl, o-methylbenzyl, p-chlorobenzyl, m-chlorobenzyl, o-chlorobenzyl, p-bromobenzyl, m-bromobenzyl, o-bromobenzyl, p-iodobenzyl, m-iodobenzyl, o-iodobenzyl, p-hydroxybenzyl, m-hydroxybenzyl, o-hydroxybenzyl, p-aminobenzyl, m-aminobenzyl, o-aminobenzyl, p-nitrobenzyl, m-nitrobenzyl, o-nitrobenzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-hydroxy-2-phenylisopropyl, and 1-chloro-2-phenylisopropyl. Of the above, preferred are benzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, and 2-phenylisopropyl. Additionally, the arylalkyl group may be optionally substituted.
[0060] Alkylsilyl—as used herein, contemplates a silyl group substituted with an alkyl group. Alkylsilyl groups may be those having 3 to 20 carbon atoms, preferably those having 3 to 10 carbon atoms. Examples of alkylsilyl groups include trimethylsilyl, triethylsilyl, methyldiethylsilyl, ethyldimethylsilyl, tripropylsilyl, tributylsilyl, triisopropylsilyl, methyldiisopropylsilyl, dimethylisopropylsilyl, tri-t-butylsilyl, triisobutylsilyl, dimethyl t-butylsilyl, and methyldi-t-butylsilyl. Additionally, the alkylsilyl group may be optionally substituted.
[0061] Arylsilyl—as used herein, contemplates a silyl group substituted with an aryl group. Arylsilyl groups may be those having 6 to 30 carbon atoms, preferably those having 8 to 20 carbon atoms. Examples of arylsilyl groups include triphenylsilyl, phenyldibiphenylylsilyl, diphenylbiphenylsilyl, phenyldiethylsilyl, diphenylethylsilyl, phenyldimethylsilyl, diphenylmethylsilyl, phenyldiisopropylsilyl, diphenylisopropylsilyl, diphenylbutylsilyl, diphenylisobutylsilyl, diphenyl t-butylsilyl. Additionally, the arylsilyl group may be optionally substituted.
[0062] Alkylgermanyl—as used herein contemplates germanyl substituted with an alkyl group. The alkylgermanyl may be those having 3 to 20 carbon atoms, preferably those having 3 to 10 carbon atoms. Examples of alkylgermanyl include trimethylgermanyl, triethylgermanyl, methyldiethylgermanyl, ethyldimethylgermanyl, tripropylgermanyl, tributylgermanyl, triisopropylgermanyl, methyldiisopropylgermanyl, dimethylisopropylgermanyl, tri-t-butylgermanyl, triisobutylgermanyl, dimethyl-t-butylgermanyl, and methyldi-t-butylgermanyl. Additionally, the alkylgermanyl may be optionally substituted.
[0063] Arylgermanyl—as used herein contemplates germanyl substituted with at least one aryl group or heteroaryl group. Arylgermanyl may be those having 6 to 30 carbon atoms, preferably those having 8 to 20 carbon atoms. Examples of arylgermanyl include triphenylgermanyl, phenyldibiphenylylgermanyl, diphenylbiphenylgermanyl, phenyldiethylgermanyl, diphenylethylgermanyl, phenyldimethylgermanyl, diphenylmethylgermanyl, phenyldiisopropylgermanyl, diphenylisopropylgermanyl, diphenylbutylgermanyl, diphenylisobutylgermanyl, and diphenyl-t-butylgermanyl. Additionally, the arylgermanyl may be optionally substituted.
[0064] The term “aza” in azadibenzofuran, azadibenzothiophene, etc. means that one or more of C—H groups in the respective aromatic fragment are replaced by a nitrogen atom. For example, azatriphenylene encompasses dibenzo[f,h]quinoxaline, dibenzo[f,h]quinoline and other analogs with two or more nitrogens in the ring system. One of ordinary skill in the art can readily envision other nitrogen analogs of the aza-derivatives described above, and all such analogs are intended to be encompassed by the terms as set forth herein.
[0065] In the present disclosure, unless otherwise defined, when any term of the group consisting of substituted alkyl, substituted cycloalkyl, substituted heteroalkyl, substituted heterocyclic group, substituted arylalkyl, substituted alkoxy, substituted aryloxy, substituted alkenyl, substituted alkynyl, substituted aryl, substituted heteroaryl, substituted alkylsilyl, substituted arylsilyl, substituted alkylgermanyl, substituted arylgermanyl, substituted amino, substituted acyl, substituted carbonyl, a substituted carboxylic acid group, a substituted ester group, substituted sulfinyl, substituted sulfonyl, and substituted phosphino is used, it means that any group of alkyl, cycloalkyl, heteroalkyl, heterocyclic group, arylalkyl, alkoxy, aryloxy, alkenyl, alkynyl, aryl, heteroaryl, alkylsilyl, arylsilyl, amino, acyl, carbonyl, a carboxylic acid group, an ester group, sulfinyl, sulfonyl, and phosphino may be substituted with one or more moieties selected from the group consisting of deuterium, halogen, unsubstituted alkyl having 1 to 20 carbon atoms, unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, unsubstituted heteroalkyl having 1 to 20 carbon atoms, an unsubstituted heterocyclic group having 3 to 20 ring atoms, unsubstituted arylalkyl having 7 to 30 carbon atoms, unsubstituted alkoxy having 1 to 20 carbon atoms, unsubstituted aryloxy having 6 to 30 carbon atoms, unsubstituted alkenyl having 2 to 20 carbon atoms, unsubstituted alkynyl having 2 to 20 carbon atoms, unsubstituted aryl having 6 to 30 carbon atoms, unsubstituted heteroaryl having 3 to 30 carbon atoms, unsubstituted alkylsilyl having 3 to 20 carbon atoms, unsubstituted arylsilyl group having 6 to 20 carbon atoms, unsubstituted alkylgermanyl having 3 to 20 carbon atoms, unsubstituted arylgermanyl having 6 to 20 carbon atoms, unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof.
[0066] It is to be understood that when a molecular fragment is described as being a substituent or otherwise attached to another moiety, its name may be written as if it were a fragment (e.g. phenyl, phenylene, naphthyl, dibenzofuryl) or as if it were the whole molecule (e.g. benzene, naphthalene, dibenzofuran). As used herein, these different ways of designating a substituent or an attached fragment are considered to be equivalent.
[0067] In the compounds mentioned in the present disclosure, hydrogen atoms may be partially or fully replaced by deuterium. Other atoms such as carbon and nitrogen may also be replaced by their other stable isotopes. The replacement by other stable isotopes in the compounds may be preferred due to its enhancements of device efficiency and stability.
[0068] In the compounds mentioned in the present disclosure, multiple substitution refers to a range that includes a di-substitution, up to the maximum available substitution. When substitution in the compounds mentioned in the present disclosure represents multiple substitution (including di-, tri-, and tetra-substitutions etc.), that means the substituent may exist at a plurality of available substitution positions on its linking structure, the substituents present at a plurality of available substitution positions may have the same structure or different structures.
[0069] In the compounds mentioned in the present disclosure, adjacent substituents in the compounds cannot be joined to form a ring unless otherwise explicitly defined, for example, adjacent substituents can be optionally joined to form a ring. In the compounds mentioned in the present disclosure, the expression that adjacent substituents can be optionally joined to form a ring includes a case where adjacent substituents may be joined to form a ring and a case where adjacent substituents are not joined to form a ring. When adjacent substituents can be optionally joined to form a ring, the ring formed may be monocyclic or polycyclic (including spirocyclic, endocyclic, fused cyclic, and etc.), as well as alicyclic, heteroalicyclic, aromatic, or heteroaromatic. In such expression, adjacent substituents may refer to substituents bonded to the same atom, substituents bonded to carbon atoms which are directly bonded to each other, or substituents bonded to carbon atoms which are more distant from each other. Preferably, adjacent substituents refer to substituents bonded to the same carbon atom and substituents bonded to carbon atoms which are directly bonded to each other.
[0070] The expression that adjacent substituents can be optionally joined to form a ring is also intended to mean that two substituents bonded to the same carbon atom are joined to each other via a chemical bond to form a ring, which can be exemplified by the following formula:
##STR00007##
[0071] The expression that adjacent substituents can be optionally joined to form a ring is also intended to mean that two substituents bonded to carbon atoms which are directly bonded to each other are joined to each other via a chemical bond to form a ring, which can be exemplified by the following formula:
##STR00008##
[0072] The expression that adjacent substituents can be optionally joined to form a ring is also intended to mean that two substituents bonded to a further distant carbon atom are joined to each other via a chemical bond to form a ring, which can be exemplified by the following formula:
##STR00009##
[0073] Furthermore, the expression that adjacent substituents can be optionally joined to form a ring is also intended to mean that, in the case where one of the two substituents bonded to carbon atoms which are directly bonded to each other represents hydrogen, the second substituent is bonded at a position at which the hydrogen atom is bonded, thereby forming a ring. This is exemplified by the following formula:
##STR00010##
[0074] According to an embodiment of the present disclosure, disclosed is a metal complex comprising a metal M and a ligand L.sub.a coordinated to the metal M, wherein the metal M is selected from a metal with a relative atomic mass greater than 40, and the ligand L.sub.a has a structure represented by Formula 1:
##STR00011##
[0075] wherein in Formula 1,
[0076] Cy is, at each occurrence identically or differently, selected from a substituted or unsubstituted aromatic ring having 6 to 24 ring atoms, a substituted or unsubstituted heteroaromatic ring having 5 to 24 ring atoms or a combination thereof;
[0077] X is selected from the group consisting of O, S, Se, NR′, CR′R′, SiR′R′ and GeR′R′, wherein when two R′ are present at the same time, the two R′ are the same or different;
[0078] X.sub.1 to X.sub.7 are, at each occurrence identically or differently, selected from C, CR.sub.x or N, and at least one of X.sub.1 to X.sub.4 is C and joined to Cy;
[0079] X.sub.1, X.sub.2, X.sub.3 or X.sub.4 is joined to the metal M by a metal-carbon bond or a metal-nitrogen bond;
[0080] A has a structure represented by Formula 2:
##STR00012##
[0081] E and F are, at each occurrence identically or differently, selected from C, CR″, N, SiR″ or GeR″;
[0082] R.sub.a1 and R.sub.a2 represent, at each occurrence identically or differently, mono-substitution, multiple substitutions or non-substitution;
[0083] the ring A.sub.1 and the ring A.sub.2 are fused through E and F;
[0084] the ring A.sub.1 and the ring A.sub.2 are, at each occurrence identically or differently, selected from an alicyclic ring having 3 to 30 ring atoms, a heterocyclic ring having 3 to 30 ring atoms, an aromatic ring having 6 to 30 ring atoms, a heteroaromatic ring having 5 to 30 ring atoms or a combination thereof;
[0085] R′, R″, R.sub.x, R.sub.a1 and R.sub.a2 are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof;
[0086] adjacent substituents R′, R″, R.sub.x, R.sub.a1, R.sub.a2 can be optionally joined to form a ring; and
[0087] “*” represents a position where A is joined.
[0088] According to an embodiment of the present disclosure, disclosed is a metal complex comprising a metal M and a ligand L.sub.a coordinated to the metal M, wherein the metal M is selected from a metal with a relative atomic mass greater than 40, and the ligand L.sub.a has a structure represented by Formula 1:
##STR00013##
[0089] wherein in Formula 1,
[0090] Cy is, at each occurrence identically or differently, selected from a substituted or unsubstituted aromatic ring having 6 to 24 ring atoms, a substituted or unsubstituted heteroaromatic ring having 5 to 24 ring atoms or a combination thereof;
[0091] X is selected from the group consisting of O, S, Se, NR′, CR′R′, SiR′R′ and GeR′R′, wherein when two R′ are present at the same time, the two R′ are the same or different;
[0092] X.sub.1 to X.sub.7 are, at each occurrence identically or differently, selected from C, CR.sub.x or N, and at least one of X.sub.1 to X.sub.4 is C and joined to the Cy;
[0093] X.sub.1, X.sub.2, X.sub.3 or X.sub.4 is joined to the metal M by a metal-carbon bond or a metal-nitrogen bond;
[0094] A has a structure represented by Formula 2:
##STR00014##
[0095] E and F are, at each occurrence identically or differently, selected from C, CR″, N, SiR″ or GeR″;
[0096] R.sub.a1 and R.sub.a2 represent, at each occurrence identically or differently, mono-substitution, multiple substitutions or non-substitution;
[0097] the ring A.sub.1 and the ring A.sub.2 are fused through E and F, and the ring A.sub.1 and the ring A.sub.2 satisfy one of the following two cases:
[0098] a first case: the ring A.sub.1 is selected from an alicyclic ring having 3 to 30 ring atoms, a heterocyclic ring having 3 to 30 ring atoms or a combination thereof; and the ring A.sub.2 is selected from an alicyclic ring having 3 to 30 ring atoms, an aromatic ring having 6 to 30 ring atoms, a heterocyclic ring having 3 to 30 ring atoms, a heteroaromatic ring having 5 to 30 ring atoms or a combination thereof;
[0099] a second case: the ring A.sub.1 is selected from an aromatic ring having 6 to 30 ring atoms, a heteroaromatic ring having 5 to 30 ring atoms or a combination thereof; and the ring A.sub.2 is selected from an alicyclic ring having 3 to 30 ring atoms, a heterocyclic ring having 3 to 30 ring atoms or a combination thereof;
[0100] R′, R″, R.sub.x, R.sub.a1 and R.sub.a2 are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof;
[0101] adjacent substituents R′, R″, R.sub.x, R.sub.a1, R.sub.a2 can be optionally joined to form a ring; and
[0102] “*” represents a position where A is joined.
[0103] In the present disclosure, the expression that “adjacent substituents R′, R″, RX, R.sub.a1, R.sub.a2 can be optionally joined to form a ring” is intended to mean that any one or more of groups of adjacent substituents, such as two substituents R′, two substituents R.sub.x, two substituents R.sub.a1, two substituents R.sub.a2, substituents R.sub.a1 and R.sub.a2, substituents R.sub.a1 and R″, substituents R.sub.a2 and R″ and substituents R′ and RX, can be joined to form a ring. Obviously, it is possible that none of these substituents are joined to form a ring.
[0104] In the present disclosure, “an alicyclic ring” is meant to include saturated alicyclic rings and unsaturated alicyclic rings except aromatic rings, where the ring contains a carbocyclic ring formed by joining three or more carbon atoms, two adjacent carbon atoms in the ring may be joined by a single, double or triple bond, and the number of rings may be one or more. Examples of alicyclic rings include, but are not limited to, saturated alicyclic rings such as a cyclopropyl ring, a cyclopentyl ring, a cyclohexyl ring, a norbornyl ring and an adamantyl ring and unsaturated alicyclic rings such as a cyclopentenyl ring, a cyclopentadienyl ring and a cyclohexenyl ring.
[0105] In the present disclosure, “ring atoms” refer to those atoms that are bonded to form a cyclic structure (such as a monocyclic (hetero)aromatic, heterocyclic or alicyclic ring or a fused (hetero)aromatic, heterocyclic or alicyclic ring). Carbon atoms and heteroatoms in the ring (including, but not limited to, O, S, N, Se, Si or Ge, etc.) are counted as ring atoms. When the ring is substituted with a substituent, atoms included in the substituent are not included in the number of ring atoms. For example, the number of ring atoms in cyclopentane, cyclopentene, tetrahydrofuran, thiophene, furan, pyrrole, imidazole, oxazole and thiazole is 5; the number of ring atoms in cyclohexane, cyclohexene, benzene, pyridine, triazine and pyrimidine is 6; the number of ring atoms in benzothiophene, benzofuran and indene is 9; the number of ring atoms in naphthalene, quinoline, isoquinoline, quinazoline and quinoxaline is 10; the number of ring atoms in dibenzothiophene, dibenzofuran, fluorene, 9,9-diphenylfluorene, azadibenzothiophene, azadibenzofuran and azafluorene is 13. Various examples described here are merely illustrative, and the same is true in other cases.
[0106] In the present disclosure, E and F shown in Formula 2 are intended to represent two adjacent atoms or groups shared by “the ring A.sub.1” and “the ring A.sub.2” when they are fused, and Formula 2 merely illustratively shows that E and F are joined. However, based on different selections of “the ring A.sub.1” and “the ring A.sub.2”, E and F may be joined by a single bond or a double bond. When E and F are joined by a double bond, E and F are both selected from C. “The ring A.sub.1” and “the ring A.sub.2” in A refer to rings including “E” and “F” in the formula, respectively, that is, when the ring A.sub.1 is mentioned, the ring A.sub.1 has the following structure:
##STR00015##
when the ring A.sub.2 is mentioned, the ring A.sub.2 has the following structure:
##STR00016##
For example, when A has the following structure:
##STR00017##
the ring A.sub.1 is a benzene ring, the ring A.sub.2 is cyclopentene, and E and F are joined by a double bond; when A has the following structure:
##STR00018##
the ring A.sub.1 is deuterated cyclohexane, the ring A.sub.2 is cyclohexane, and E and F are joined by a single bond; when A has the following structure:
##STR00019##
the ring A.sub.1 is deuterated cyclohexene, the ring A.sub.2 is a benzene ring, E and F are joined by a double bond. Various examples described here are merely illustrative, and the same is true in other cases.
[0107] According to an embodiment of the present disclosure, two adjacent substituents R.sub.a2 are not joined to form a ring.
[0108] According to an embodiment of the present disclosure, when Formula 2 has the following structure:
##STR00020##
the ring formed by joined two adjacent substituents R.sub.a2 is not an aromatic ring or a heteroaromatic ring, or two adjacent substituents R.sub.a2 are not joined to form a ring.
[0109] According to an embodiment of the present disclosure, Cy is selected from any structure in the group consisting of the following:
##STR00021##
[0110] wherein
[0111] R represents, at each occurrence identically or differently, mono-substitution, multiple substitutions or non-substitution; and when multiple R are present at the same time in any structure, the multiple R are the same or different;
[0112] R is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof;
[0113] adjacent substituents R can be optionally joined to form a ring;
[0114] wherein “#” represents a position where Cy is joined to the metal M, and
##STR00022##
represents a position where Cy is joined to X.sub.1, X.sub.2, X.sub.3 or X.sub.4.
[0115] In the present disclosure, the expression that “adjacent substituents R can be optionally joined to form a ring” is intended to mean that any one or more of groups of any two adjacent substituents R can be joined to form a ring. Obviously, it is possible that none of these substituents are joined to form a ring.
[0116] According to an embodiment of the present disclosure, L.sub.a is, at each occurrence identically or differently, selected from the group consisting of the following:
##STR00023## ##STR00024## ##STR00025## ##STR00026## ##STR00027## ##STR00028## ##STR00029## ##STR00030## ##STR00031## ##STR00032## ##STR00033##
[0117] wherein
[0118] X is selected from the group consisting of O, S, Se, NR′, CR′R′, SiR′R′ and GeR′R′, wherein when two R′ are present at the same time, the two R′ are the same or different;
[0119] R and R.sub.x represent, at each occurrence identically or differently, mono-substitution, multiple substitutions or non-substitution;
[0120] A has a structure represented by Formula 2:
##STR00034##
[0121] E and F are, at each occurrence identically or differently, selected from C, CR″, N, SiR″ or GeR″;
[0122] R.sub.a1 and R.sub.a2 represent, at each occurrence identically or differently, mono-substitution, multiple substitutions or non-substitution;
[0123] the ring A.sub.1 and the ring A.sub.2 are fused through E and F, and the ring A.sub.1 and the ring A.sub.2 satisfy one of the following two cases:
[0124] the first case: the ring A.sub.1 is selected from an alicyclic ring having 3 to 30 ring atoms, a heterocyclic ring having 3 to 30 ring atoms or a combination thereof; and the ring A.sub.2 is selected from an alicyclic ring having 3 to 30 ring atoms, an aromatic ring having 6 to 30 ring atoms, a heterocyclic ring having 3 to 30 ring atoms, a heteroaromatic ring having 5 to 30 ring atoms or a combination thereof;
[0125] the second case: the ring A.sub.1 is selected from an aromatic ring having 6 to 30 ring atoms, a heteroaromatic ring having 5 to 30 ring atoms or a combination thereof; and the ring A.sub.2 is selected from an alicyclic ring having 3 to 30 ring atoms, a heterocyclic ring having 3 to 30 ring atoms or a combination thereof;
[0126] “*” represents a position where A is joined;
[0127] R, R′, R″, R.sub.x, R.sub.a1 and R.sub.a2 are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof;
[0128] adjacent substituents R, R′, R″, RX, R.sub.a1, R.sub.a2 can be optionally joined to form a ring.
[0129] In the present disclosure, the expression that “adjacent substituents R, R′, R″, R.sub.x, R.sub.a1, R.sub.a2 can be optionally joined to form a ring” is intended to mean that any one or more of groups of adjacent substituents, such as two substituents R, two substituents R′, two substituents R.sub.x, two substituents R.sub.a1, two substituents R.sub.a2, substituents R.sub.a1 and R.sub.a2, substituents R.sub.a1 and R″, substituents R.sub.a2 and R″ and substituents R′ and RX, can be joined to form a ring. Obviously, it is possible that none of these substituents are joined to form a ring.
[0130] According to an embodiment of the present disclosure, the metal complex has a general formula of M(L.sub.a).sub.m(L.sub.b).sub.n(L.sub.c).sub.q;
[0131] wherein
[0132] M is, at each occurrence identically or differently, selected from the group consisting of Cu, Ag, Au, Ru, Rh, Pd, Os, Ir and Pt;
[0133] L.sub.a, L.sub.b and L.sub.c are a first ligand, a second ligand and a third ligand coordinated to the metal M, respectively, and L.sub.c is the same as or different from L.sub.a or L.sub.b; wherein L.sub.a, L.sub.b and L.sub.c can be optionally joined to form a multidentate ligand; for example, any two of L.sub.a, L.sub.b and L.sub.c may be joined to form a tetradentate ligand; in another example, L.sub.a, L.sub.b and L.sub.c may be joined to each other to form a hexadentate ligand; in another example, none of L.sub.a, L.sub.b and L.sub.c are joined so that no multidentate ligand is formed;
[0134] m is selected from 1, 2 or 3, n is selected from 0, 1 or 2, q is selected from 0, 1 or 2, and m+n+q equals an oxidation state of the metal M; wherein when m is greater than or equal to 2, multiple L.sub.a are the same or different; when n is equal to 2, two L.sub.b are the same or different; when q is equal to 2, two L.sub.c are the same or different;
[0135] L.sub.b and L.sub.c are, at each occurrence identically or differently, selected from a structure represented by any one of the group consisting of the following:
##STR00035##
[0136] wherein
[0137] R.sub.a and R.sub.b represent, at each occurrence identically or differently, mono-substitution, multiple substitutions or non-substitution;
[0138] X.sub.b is, at each occurrence identically or differently, selected from the group consisting of O, S, Se, NR.sub.N1 and CR.sub.C1R.sub.C2;
[0139] R.sub.a, R.sub.b, R.sub.c, R.sub.N1, R.sub.C1 and R.sub.C2 are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof; and
[0140] adjacent substituents R.sub.a, R.sub.b, R.sub.c, R.sub.N1, R.sub.C1 and R.sub.C2 can be optionally joined to form a ring.
[0141] In the present disclosure, the expression that “adjacent substituents R.sub.a, R.sub.b, R.sub.c, R.sub.N1, R.sub.C1 and R.sub.C2 can be optionally joined to form a ring” is intended to mean that any one or more of groups of adjacent substituents, such as two substituents R.sub.a, two substituents R.sub.b, substituents R.sub.a and R.sub.b, substituents R.sub.a and R.sub.c, substituents R.sub.b and R.sub.c, substituents R.sub.a and R.sub.N1, substituents R.sub.b and R.sub.N1, substituents R.sub.a and R.sub.C1, substituents R.sub.a and R.sub.C2, substituents R.sub.b and R.sub.C1, substituents R.sub.b and R.sub.C2 and substituents R.sub.C1 and R.sub.C2, can be joined to form a ring. Obviously, it is possible that none of these substituents are joined to form a ring.
[0142] According to an embodiment of the present disclosure, the metal M is, at each occurrence identically or differently, selected from the group consisting of Cu, Ag, Au, Ru, Rh, Pd, Os, Ir and Pt.
[0143] According to an embodiment of the present disclosure, the metal M is, at each occurrence identically or differently, selected from Pt or Ir.
[0144] According to an embodiment of the present disclosure, the metal complex Ir(L.sub.a).sub.m(L.sub.b).sub.3-m has a structure represented by Formula 3:
##STR00036##
[0145] wherein
[0146] m is selected from 1, 2 or 3; when m is selected from 1, two L.sub.b are the same or different; when m is selected from 2 or 3, multiple L.sub.a are the same or different;
[0147] Y.sub.1 to Y.sub.4 are, at each occurrence identically or differently, selected from CR.sub.y or N;
[0148] X is selected from the group consisting of O, S, Se, NR′, SiR′R′ and GeR′R′, wherein when two R′ are present at the same time, the two R′ are the same or different;
[0149] X.sub.3 to X.sub.7 are, at each occurrence identically or differently, selected from CR.sub.x or N;
[0150] A has a structure represented by Formula 2:
##STR00037##
[0151] E and F are, at each occurrence identically or differently, selected from C, CR″, N, SiR″ or GeR″;
[0152] R.sub.a1 and R.sub.a2 represent, at each occurrence identically or differently, mono-substitution, multiple substitutions or non-substitution;
[0153] the ring A.sub.1 and the ring A.sub.2 are fused through E and F, and the ring A.sub.1 and the ring A.sub.2 satisfy one of the following two cases:
[0154] the first case: the ring A.sub.1 is selected from an alicyclic ring having 3 to 30 ring atoms, a heterocyclic ring having 3 to 30 ring atoms or a combination thereof; and the ring A.sub.2 is selected from an alicyclic ring having 3 to 30 ring atoms, an aromatic ring having 6 to 30 ring atoms, a heterocyclic ring having 3 to 30 ring atoms, a heteroaromatic ring having 5 to 30 ring atoms or a combination thereof;
[0155] the second case: the ring A.sub.1 is selected from an aromatic ring having 6 to 30 ring atoms, a heteroaromatic ring having 5 to 30 ring atoms or a combination thereof; and the ring A.sub.2 is selected from an alicyclic ring having 3 to 30 ring atoms, a heterocyclic ring having 3 to 30 ring atoms or a combination thereof;
[0156] R′, R″, R.sub.x, R.sub.y, R.sub.a1, R.sub.a2 and R.sub.1 to R.sub.8 are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof;
[0157] adjacent substituents R′, R″, R.sub.x, R.sub.y, R.sub.a1, R.sub.a2 can be optionally joined to form a ring;
[0158] adjacent substituents R.sub.1 to R.sub.8 can be optionally joined to form a ring; and
[0159] “*” represents a position where A is joined.
[0160] In the present disclosure, the expression that “adjacent substituents R′, R″, R.sub.x, R.sub.y, R.sub.a1, R.sub.a2 can be optionally joined to form a ring” is intended to mean that any one or at least two of groups of adjacent substituents, such as two substituents R′, two substituents R.sub.x, two substituents R.sub.y, two substituents R.sub.a1, two substituents R.sub.a2, substituents R′ and R.sub.x, substituents R.sub.a1 and R.sub.a2, substituents R.sub.a1 and R″ and substituents R.sub.a2 and R″ can be joined to form a ring. Obviously, it is possible that none of these substituents are joined to form a ring.
[0161] In the present disclosure, the expression that “adjacent substituents R.sub.1 to R.sub.8 can be optionally joined to form a ring” is intended to mean that any one or at least two of groups of adjacent substituents, such as adjacent substituents R.sub.1 and R.sub.2, adjacent substituents R.sub.3 and R.sub.2, adjacent substituents R.sub.3 and R.sub.4, adjacent substituents R.sub.5 and R.sub.4, adjacent substituents R.sub.5 and R.sub.6, adjacent substituents R.sub.7 and R.sub.6 and adjacent substituents R.sub.7 and R.sub.8, can be joined to form a ring. Obviously, it is possible that none of these substituents are joined to form a ring.
[0162] According to an embodiment of the present disclosure, the metal complex Ir(L.sub.a).sub.m(L.sub.b).sub.3-m has a structure represented by Formula 3A:
##STR00038##
[0163] wherein
[0164] m is selected from 1, 2 or 3; when m is selected from 1, two L.sub.b are the same or different; when m is selected from 2 or 3, multiple L.sub.a are the same or different;
[0165] X is selected from the group consisting of O, S, Se, NR′, CR′R′, SiR′R′ and GeR′R′, wherein when two R′ are present at the same time, the two R′ are the same or different;
[0166] R.sub.x and R.sub.y represent, at each occurrence identically or differently, mono-substitution, multiple substitutions or non-substitution;
[0167] A has a structure represented by Formula 2:
##STR00039##
[0168] E and F are, at each occurrence identically or differently, selected from C, CR″, N, SiR″ or GeR″;
[0169] R.sub.a1 and R.sub.a2 represent, at each occurrence identically or differently, mono-substitution, multiple substitutions or non-substitution;
[0170] the ring A.sub.1 and the ring A.sub.2 are fused through E and F, and the ring A.sub.1 and the ring A.sub.2 satisfy one of the following two cases:
[0171] the first case: the ring A.sub.1 is selected from an alicyclic ring having 3 to 30 ring atoms, a heterocyclic ring having 3 to 30 ring atoms or a combination thereof; and the ring A.sub.2 is selected from an alicyclic ring having 3 to 30 ring atoms, an aromatic ring having 6 to 30 ring atoms, a heterocyclic ring having 3 to 30 ring atoms, a heteroaromatic ring having 5 to 30 ring atoms or a combination thereof;
[0172] the second case: the ring A.sub.1 is selected from an aromatic ring having 6 to 30 ring atoms, a heteroaromatic ring having 5 to 30 ring atoms or a combination thereof; and the ring A.sub.2 is selected from an alicyclic ring having 3 to 30 ring atoms, a heterocyclic ring having 3 to 30 ring atoms or a combination thereof;
[0173] R′, R″, R.sub.x, R.sub.y, R.sub.a1, R.sub.a2 and R.sub.1 to R.sub.8 are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof;
[0174] adjacent substituents R′, R″, R.sub.x, R.sub.y, R.sub.a1, R.sub.a2 can be optionally joined to form a ring;
[0175] adjacent substituents R.sub.1 to R.sub.8 can be optionally joined to form a ring; and
[0176] “*” represents a position where A is joined.
[0177] According to an embodiment of the present disclosure, wherein, X is selected from O or S.
[0178] According to an embodiment of the present disclosure, wherein, X is O.
[0179] According to an embodiment of the present disclosure, wherein, X.sub.1 to X.sub.7 are, at each occurrence identically or differently, selected from C or CR.sub.x.
[0180] According to an embodiment of the present disclosure, wherein, at least one of X.sub.1 to X.sub.7 is N, for example, one of X.sub.1 to X.sub.7 is N or two of X.sub.1 to X.sub.7 are N.
[0181] According to an embodiment of the present disclosure, in Formula 3, X.sub.3 to X.sub.7 are, at each occurrence identically or differently, selected from CR.sub.x.
[0182] According to an embodiment of the present disclosure, in Formula 3, at least one of X.sub.3 to X.sub.7 is N, for example, one of X.sub.3 to X.sub.7 is N or two of X.sub.3 to X.sub.7 are N.
[0183] According to an embodiment of the present disclosure, wherein, Y.sub.1 to Y.sub.4 are, at each occurrence identically or differently, selected from CR.sub.y.
[0184] According to an embodiment of the present disclosure, wherein, at least one of Y.sub.1 to Y.sub.4 is N, for example, one of Y.sub.1 to Y.sub.4 is N or two of Y.sub.1 to Y.sub.4 are N.
[0185] According to an embodiment of the present disclosure, wherein, R.sub.x is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 20 carbon atoms, cyano and combinations thereof.
[0186] According to an embodiment of the present disclosure, wherein, R.sub.x is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, fluorine, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms, substituted or unsubstituted aryl having 6 to 12 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 12 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 6 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 6 carbon atoms, cyano and combinations thereof.
[0187] According to an embodiment of the present disclosure, wherein, R.sub.x is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, fluorine, cyano, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, cyclopentyl, cyclohexyl, deuterated methyl, deuterated ethyl, deuterated propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated t-butyl, deuterated cyclopentyl, deuterated cyclohexyl, phenyl, pyridyl, trimethylsilyl, trimethylgermanyl and combinations thereof.
[0188] According to an embodiment of the present disclosure, wherein, at least one of X.sub.1 to X.sub.7 is selected from CR.sub.x, and the R.sub.x is cyano or fluorine.
[0189] According to an embodiment of the present disclosure, wherein, at least one of X.sub.3 to X.sub.7 is selected from CR.sub.x, and the R.sub.x is cyano or fluorine.
[0190] According to an embodiment of the present disclosure, wherein, at least one of X.sub.5 to X.sub.7 is selected from CR.sub.x, and the R.sub.x is cyano or fluorine.
[0191] According to an embodiment of the present disclosure, wherein, X.sub.7 is selected from CR.sub.x, and the R.sub.x is cyano or fluorine.
[0192] According to an embodiment of the present disclosure, wherein, the ring A.sub.1 is selected from an alicyclic ring having 3 to 10 ring atoms, a heterocyclic ring having 3 to 10 ring atoms or a combination thereof; and the ring A.sub.2 is selected from an alicyclic ring having 3 to 10 ring atoms, an aromatic ring having 6 to 18 ring atoms, a heterocyclic ring having 3 to 10 ring atoms, a heteroaromatic ring having 5 to 18 ring atoms or a combination thereof.
[0193] According to an embodiment of the present disclosure, wherein, the ring A.sub.1 is selected from the group consisting of: cyclopentane, cyclopentene, cyclohexane, cyclohexene, cycloheptane, cycloheptene, and the following groups containing one heteroatom or at least two heteroatoms of nitrogen, oxygen, sulfur, selenium, silicon and germanium: heterocyclopentane, heterocyclopentene, heterocyclohexane, heterocyclohexene, heterocycloheptane and heterocycloheptene; and the ring A.sub.2 is selected from the group consisting of: benzene, naphthalene, phenanthrene, triphenylene, pyridine, pyrimidine, pyrazine, pyridazine, triazine, pyrrole, furan, thiophene, imidazole, thiazole, oxazole, cyclopentane, cyclopentene, cyclohexane, cyclohexene, cycloheptane, cycloheptene and the following groups containing one heteroatom or at least two heteroatoms of nitrogen, oxygen, sulfur, selenium, silicon and germanium: heterocyclopentane, heterocyclopentene, heterocyclohexane, heterocyclohexene, heterocycloheptane and heterocycloheptene.
[0194] According to an embodiment of the present disclosure, wherein, the ring A.sub.1 is selected from an aromatic ring having 6 to 18 ring atoms, a heteroaromatic ring having 5 to 18 ring atoms or a combination thereof; and the ring A.sub.2 is selected from an alicyclic ring having 3 to 10 ring atoms, a heterocyclic ring having 3 to 10 ring atoms or a combination thereof.
[0195] According to an embodiment of the present disclosure, wherein, the ring A.sub.1 is selected from benzene, naphthalene, phenanthrene, triphenylene, pyridine, pyrimidine, pyrazine, pyridazine, triazine, pyrrole, furan, thiophene, imidazole, thiazole or oxazole; and the ring A.sub.2 is selected from cyclopentane, cyclopentene, cyclohexane, cyclohexene, cycloheptane, cycloheptene or the following groups containing one heteroatom or at least two heteroatoms of nitrogen, oxygen, sulfur, selenium, silicon and germanium: heterocyclopentane, heterocyclopentene, heterocyclohexane, heterocyclohexene, heterocycloheptane and heterocycloheptene.
[0196] According to an embodiment of the present disclosure, wherein, the ring A.sub.1 is selected from benzene; and the ring A.sub.2 is selected from cyclopentene, cyclohexene or cycloheptene.
[0197] According to an embodiment of the present disclosure, wherein, the ring A.sub.1 is selected from cyclopentene, cyclohexene or cycloheptene; and the ring A.sub.2 is selected from benzene.
[0198] According to an embodiment of the present disclosure, wherein, R.sub.a1 and R.sub.a2 are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, a hydroxyl group, a sulfanyl group, a cyano group and combinations thereof.
[0199] According to an embodiment of the present disclosure, wherein, R.sub.a1 and R.sub.a2 are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, fluorine, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms, substituted or unsubstituted aryl having 6 to 18 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 18 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 15 carbon atoms, cyano and combinations thereof.
[0200] According to an embodiment of the present disclosure, wherein, R.sub.a1 and R.sub.a2 are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms, cyano and combinations thereof.
[0201] According to an embodiment of the present disclosure, wherein, R.sub.a1 and R.sub.a2 are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, fluorine, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, cyclopentyl, cyclohexyl, deuterated methyl, deuterated ethyl, deuterated propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated t-butyl, deuterated cyclopentyl, deuterated cyclohexyl, phenyl, pyridyl, trimethylsilyl, cyano and combinations thereof.
[0202] According to an embodiment of the present disclosure, wherein, A is, at each occurrence identically or differently, selected from the group consisting of A-1 to A-264, wherein the specific structures of A-1 to A-264 are referred to claim 13.
[0203] According to an embodiment of the present disclosure, hydrogens in A-1 to A-264 can be partially or fully deuterated, and the specific structures of A-1 to A-264 are referred to claim 13.
[0204] According to an embodiment of the present disclosure, in Formula 3 and Formula 3A, R.sub.y is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms and combinations thereof.
[0205] According to an embodiment of the present disclosure, wherein, in Formula 3 and Formula 3A, R.sub.y is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, fluorine, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms, substituted or unsubstituted aryl having 6 to 12 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 11 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 6 carbon atoms, cyano and combinations thereof.
[0206] According to an embodiment of the present disclosure, wherein, in Formula 3 and Formula 3A, R.sub.y is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, cyclopentyl, cyclohexyl, deuterated methyl, deuterated ethyl, deuterated propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated t-butyl, deuterated cyclopentyl, deuterated cyclohexyl, phenyl, pyridyl, trimethylsilyl and combinations thereof.
[0207] According to an embodiment of the present disclosure, in Formula 3 and Formula 3A, at least one R.sub.y is selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms and combinations thereof.
[0208] According to an embodiment of the present disclosure, R.sub.7 is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof.
[0209] According to an embodiment of the present disclosure, in Formula 3 and Formula 3A, at least one or at least two of R.sub.5 to R.sub.8 are selected from substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms or a combination thereof; and the total number of carbon atoms in all of R.sub.5 to R.sub.8 is at least 4.
[0210] According to an embodiment of the present disclosure, in Formula 3 and Formula 3A, at least one or at least two of R.sub.6 and R.sub.7 are selected from substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms or a combination thereof, and the total number of carbon atoms in both of R.sub.6 and R.sub.7 is at least 4.
[0211] According to an embodiment of the present disclosure, in Formula 3 and Formula 3A, at least one, at least two, at least three or all of R.sub.2, R.sub.3, R.sub.6 and R.sub.7 are selected from the group consisting of: deuterium, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms and combinations thereof.
[0212] According to an embodiment of the present disclosure, in Formula 3 and Formula 3A, at least one, at least two, at least three or all of R.sub.2, R.sub.3, R.sub.6 and R.sub.7 are selected from the group consisting of: deuterium, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms and combinations thereof.
[0213] According to an embodiment of the present disclosure, in Formula 3 and Formula 3A, at least one, at least two, at least three or all of R.sub.2, R.sub.3, R.sub.6 and R.sub.7 are selected from the group consisting of: deuterium, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, cyclopentyl, cyclohexyl and combinations thereof; optionally, hydrogens in the above groups can be partially or fully deuterated.
[0214] According to an embodiment of the present disclosure, R′ is, at each occurrence identically or differently, selected from substituted or unsubstituted alkyl having 1 to 20 carbon atoms or substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms.
[0215] According to an embodiment of the present disclosure, R″ is, at each occurrence identically or differently, selected from hydrogen, deuterium, substituted or unsubstituted alkyl having 1 to 20 carbon atoms or substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms.
[0216] According to an embodiment of the present disclosure, R′ is, at each occurrence identically or differently, selected from methyl or deuterated methyl.
[0217] According to an embodiment of the present disclosure, L.sub.a is, at each occurrence identically or differently, selected from the group consisting of: L.sub.a1-1 to L.sub.a1-497, L.sub.a2-1 to L.sub.a2-485, L.sub.a3-1 to L.sub.a3-485 and L.sub.a4-1 to L.sub.a4-226, wherein the specific structures of L.sub.a1-1 to L.sub.a1-497, L.sub.a2-1 to L.sub.a2-485, L.sub.a3-1 to L.sub.a3-485 and L.sub.a4-1 to L.sub.a4-226 are referred to claim 17.
[0218] According to an embodiment of the present disclosure, hydrogens in the structures of L.sub.a1-1 to L.sub.a1-497, L.sub.a2-1 to L.sub.a2-485, L.sub.a3-1 to L.sub.a3-485 and L.sub.a4-1 to L.sub.a4-226 can be partially or fully deuterated, wherein the specific structures of L.sub.a1-1 to L.sub.a1-497, L.sub.a2-1 to L.sub.a2-485, L.sub.a3-1 to L.sub.a3-485 and L.sub.a4-1 to L.sub.a4-226 are referred to claim 17.
[0219] According to an embodiment of the present disclosure, L.sub.b is, at each occurrence identically or differently, selected from the group consisting of L.sub.b1 to L.sub.b329, wherein the specific structures of L.sub.b1 to L.sub.b329 are referred to claim 18.
[0220] According to an embodiment of the present disclosure, hydrogens in the structures of L.sub.b1 to L.sub.b329 can be partially or fully deuterated, wherein the specific structures of L.sub.b1 to L.sub.b329 are referred to claim 18.
[0221] According to an embodiment of the present disclosure, L.sub.c is, at each occurrence identically or differently, selected from the group consisting of L.sub.c1 to L.sub.c360, wherein the specific structures of L.sub.c1 to L.sub.360 are referred to claim 19.
[0222] According to an embodiment of the present disclosure, the metal complex has a structure of Ir(L.sub.a).sub.2(L.sub.b), wherein L.sub.a is, at each occurrence identically or differently, selected from any one or any two of the group consisting of L.sub.a1-1 to L.sub.a1-497, L.sub.a2-1 to L.sub.a2-485, L.sub.a3-1 to L.sub.a3-485 and L.sub.a4-1 to L.sub.a4-226, and L.sub.b is selected from any one of the group consisting of L.sub.b1 to L.sub.b329, wherein the specific structures of L.sub.a1-1 to L.sub.a1-497, L.sub.a2-1 to L.sub.a2-485, L.sub.a3-1 to L.sub.a3-485 and L.sub.a4-1 to L.sub.a4-226 are referred to claim 17 and the specific structures of L.sub.b1 to L.sub.b329 are referred to claim 18.
[0223] According to an embodiment of the present disclosure, the metal complex has a structure of Ir(L.sub.a)(L.sub.b).sub.2, wherein L.sub.a is, at each occurrence identically or differently, selected from any one of the group consisting of L.sub.a1-1 to L.sub.a1-497, L.sub.a2-1 to L.sub.a2-485, L.sub.a3-1 to L.sub.a3-485 and L.sub.a4-1 to L.sub.a4-226, and L.sub.b is selected from any one or any two of the group consisting of L.sub.b1 to L.sub.b329, wherein the specific structures of L.sub.a1-1 to L.sub.a1-497, L.sub.a2-1 to L.sub.a2-485, L.sub.a3-1 to L.sub.a3-485 and L.sub.a4-1 to L.sub.a4-226 are referred to claim 17 and the specific structures of L.sub.b1 to L.sub.b329 are referred to claim 18.
[0224] According to an embodiment of the present disclosure, the metal complex has a structure of Ir(L.sub.a).sub.3, wherein L.sub.a is, at each occurrence identically or differently, selected from any one or any two or any three of the group consisting of L.sub.a1-1 to L.sub.a1-497, L.sub.a2-1 to L.sub.a2-485, L.sub.a3-1 to L.sub.a3-485 and L.sub.a4-1 to L.sub.a4-226, wherein the specific structures of L.sub.a1-1 to L.sub.a1-497, L.sub.a2-1 to L.sub.a2-485, L.sub.a3-1 to L.sub.a3-485 and L.sub.a4-1 to L.sub.a4-226 are referred to claim 17.
[0225] According to an embodiment of the present disclosure, the metal complex has a structure of Ir(L.sub.a).sub.2(L.sub.c), wherein L.sub.a is, at each occurrence identically or differently, selected from any one or any two of the group consisting of L.sub.a1-1 to L.sub.a1-497, L.sub.a2-1 to L.sub.a2-485, L.sub.a3-1 to L.sub.a3-485 and L.sub.a4-1 to L.sub.a4-226, and L.sub.c is selected from any one of the group consisting of L.sub.c1 to L.sub.360, wherein the specific structures of L.sub.a1-1 to L.sub.a1-497, L.sub.a2-1 to L.sub.a2-485, L.sub.a3-1 to L.sub.a3-485 and L.sub.a4-1 to L.sub.a4-226 are referred to claim 17 and the specific structures of L.sub.c1 to L.sub.360 are referred to claim 19.
[0226] According to an embodiment of the present disclosure, the metal complex has a structure of Ir(L.sub.a)(L.sub.c).sub.2, wherein L.sub.a is, at each occurrence identically or differently, selected from any one of the group consisting of L.sub.a1-1 to L.sub.a1-497, L.sub.a2-1 to L.sub.a2-485, L.sub.a3-1 to L.sub.a3-485 and L.sub.a4-1 to L.sub.a4-226, and L.sub.c is selected from any one or any two of the group consisting of L.sub.c1 to L.sub.360, wherein the specific structures of L.sub.a1-1 to L.sub.a1-497, L.sub.a2-1 to L.sub.a2-485, L.sub.a3-1 to L.sub.a3-485 and L.sub.a4-1 to L.sub.a4-226 are referred to claim 17 and the specific structures of L.sub.c1 to L.sub.360 are referred to claim 19.
[0227] According to an embodiment of the present disclosure, the metal complex has a structure of Ir(L.sub.a)(L.sub.b)(L.sub.c), wherein L.sub.a is, at each occurrence identically or differently, selected from any one of the group consisting of L.sub.a1-1 to L.sub.a1-497, L.sub.a2-1 to L.sub.a2-485, L.sub.a3-1 to L.sub.a3-485 and L.sub.a4-1 to L.sub.a4-226, L.sub.b is selected from any one of the group consisting of L.sub.b1 to L.sub.b329, and L.sub.c is selected from any one of the group consisting of L.sub.c1 to L.sub.360, wherein the specific structures of L.sub.a1-1 to L.sub.a1-497, L.sub.a2-1 to L.sub.a2-485, L.sub.a3-1 to L.sub.a3-485 and L.sub.a4-1 to L.sub.a4-226 are referred to claim 17, the specific structures of L.sub.b1 to L.sub.b329 are referred to claim 18, and the specific structures of L.sub.c1 to L.sub.c360 are referred to claim 19.
[0228] According to an embodiment of the present disclosure, the metal complex is selected from the group consisting of Metal Complex 1 to Metal Complex 2454, wherein the specific structures of Metal Complex 1 to Metal Complex 2454 are referred to claim 20.
[0229] According to an embodiment of the present disclosure, hydrogens in the structures of Metal Complex 1 to Metal Complex 2454 can be partially or fully deuterated, wherein the specific structures of Metal Complex 1 to Metal Complex 2454 are referred to claim 20.
[0230] According to an embodiment of the present disclosure, disclosed is an electroluminescent device. The electroluminescent device comprises:
[0231] an anode,
[0232] a cathode, and
[0233] an organic layer disposed between the anode and the cathode, wherein the organic layer comprises the metal complex in any one of the preceding embodiments.
[0234] According to an embodiment of the present disclosure, in the electroluminescent device, the organic layer comprising the metal complex is a light-emitting layer.
[0235] According to an embodiment of the present disclosure, the electroluminescent device emits green light.
[0236] According to an embodiment of the present disclosure, the electroluminescent device emits white light.
[0237] According to an embodiment of the present disclosure, in the electroluminescent device, the light-emitting layer comprises a first host compound.
[0238] According to an embodiment of the present disclosure, in the electroluminescent device, the light-emitting layer comprises a first host compound and a second host compound.
[0239] According to an embodiment of the present disclosure, in the electroluminescent device, the first host compound and/or the second host compound comprise at least one chemical group selected from the group consisting of: benzene, pyridine, pyrimidine, triazine, carbazole, azacarbazole, indolocarbazole, dibenzothiophene, aza-dibenzothiophene, dibenzofuran, azadibenzofuran, dibenzoselenophene, triphenylene, azatriphenylene, fluorene, silafluorene, naphthalene, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene, azaphenanthrene and combinations thereof.
[0240] According to an embodiment of the present disclosure, the first host compound has a structure represented by Formula 4:
##STR00040##
[0241] wherein
[0242] E.sub.1 to E.sub.6 are, at each occurrence identically or differently, selected from C, CR.sub.e or N, at least two of E.sub.1 to E.sub.6 are N, and at least one of E.sub.1 to E.sub.6 is C and joined to Formula A;
##STR00041##
[0243] wherein
[0244] Q is, at each occurrence identically or differently, selected from the group consisting of O, S, Se, N, NR′″, CR′″R′″, SiR′″R′″, GeR′″R′″ and R′″C═CR′″; when two R′″ are present at the same time, the two R′″ may be the same or different;
[0245] p is 0 or 1; r is 0 or 1;
[0246] when Q is selected from N, p is 0 and r is 1;
[0247] when Q is selected from the group consisting of O, S, Se, NR′″, CR′″R′″, SiR′″R′″, GeR′″R′″ and R′″C═CR′″, p is 1 and r is 0;
[0248] L is, at each occurrence identically or differently, selected from a single bond, substituted or unsubstituted alkylene having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkylene having 3 to 20 carbon atoms, substituted or unsubstituted arylene having 6 to 20 carbon atoms, substituted or unsubstituted heteroarylene having 3 to 20 carbon atoms or a combination thereof;
[0249] Q.sub.1 to Q.sub.8 are, at each occurrence identically or differently, selected from C, CR.sub.q or N;
[0250] R.sub.e, R′″ and R.sub.q are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof;
[0251] “*” represents a position where Formula A is joined to Formula 4; and
[0252] adjacent substituents R.sub.e, R′″, R.sub.q can be optionally joined to form a ring.
[0253] In the present disclosure, the expression that “adjacent substituents R.sub.e, R′″, R.sub.q can be optionally joined to form a ring” is intended to mean that any one or at least two of groups of adjacent substituents, such as two substituents R.sub.e, two substituents R′″, substituents R.sub.q and substituents R′″ and R.sub.q, can be joined to form a ring. Obviously, it is possible that none of these substituents are joined to form a ring.
[0254] According to an embodiment of the present disclosure, Q is, at each occurrence identically or differently, selected from O, S, N or NR′″.
[0255] According to an embodiment of the present disclosure, E.sub.1 to E.sub.6 are, at each occurrence identically or differently, selected from C, CR.sub.e or N, three of E.sub.1 to E.sub.6 are N, at least one of E.sub.1 to E.sub.6 is CR.sub.e, and R.sub.e is, at each occurrence identically or differently, selected from the group consisting of: substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms and combinations thereof.
[0256] According to an embodiment of the present disclosure, E.sub.1 to E.sub.6 are, at each occurrence identically or differently, selected from C, CR.sub.e or N, three of E.sub.1 to E.sub.6 are N, at least one of E.sub.1 to E.sub.6 is CR.sub.e, and R.sub.e is, at each occurrence identically or differently, selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuryl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted carbazolyl or a combination thereof.
[0257] According to an embodiment of the present disclosure, R.sub.e is, at each occurrence identically or differently, selected from the group consisting of: substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms and combinations thereof.
[0258] According to an embodiment of the present disclosure, R.sub.e is, at each occurrence identically or differently, selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuryl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted carbazolyl or a combination thereof.
[0259] According to an embodiment of the present disclosure, at least one or at least two of Q.sub.1 to Q.sub.8 are selected from CR.sub.q, and R.sub.q is selected from substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 5 to 30 carbon atoms or a combination thereof.
[0260] According to an embodiment of the present disclosure, at least one or at least two of Q.sub.1 to Q.sub.8 are selected from CR.sub.q, and R.sub.q is selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted pyridyl or a combination thereof.
[0261] According to an embodiment of the present disclosure, R′″ is, at each occurrence identically or differently, selected from the group consisting of: substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms and combinations thereof.
[0262] According to an embodiment of the present disclosure, R′″ is, at each occurrence identically or differently, selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuryl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted carbazolyl or a combination thereof.
[0263] According to an embodiment of the present disclosure, L is, at each occurrence identically or differently, selected from a single bond, substituted or unsubstituted arylene having 6 to 20 carbon atoms, substituted or unsubstituted heteroarylene having 3 to 20 carbon atoms or a combination thereof.
[0264] According to an embodiment of the present disclosure, L is, at each occurrence identically or differently, selected from a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted carbazolylene, substituted or unsubstituted dibenzofurylene, substituted or unsubstituted dibenzothienylene or substituted or unsubstituted fluorenylidene.
[0265] According to an embodiment of the present disclosure, L is, at each occurrence identically or differently, selected from a single bond, substituted or unsubstituted phenylene or substituted or unsubstituted biphenylene.
[0266] According to an embodiment of the present disclosure, the first host compound is selected from the group consisting of H-1 to H-243, wherein the specific structures of H-1 to H-243 are referred to claim 25.
[0267] According to an embodiment of the present disclosure, in the electroluminescent device, the second host compound has a structure represented by Formula 5:
##STR00042##
[0268] wherein
[0269] L.sub.x is, at each occurrence identically or differently, selected from a single bond, substituted or unsubstituted alkylene having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkylene having 3 to 20 carbon atoms, substituted or unsubstituted arylene having 6 to 20 carbon atoms, substituted or unsubstituted heteroarylene having 3 to 20 carbon atoms or a combination thereof;
[0270] V is, at each occurrence identically or differently, selected from C, CR.sub.v or N, and at least one of V is C and joined to L.sub.x;
[0271] U is, at each occurrence identically or differently, selected from C, CR.sub.u or N, and at least one of U is C and joined to L.sub.x;
[0272] R.sub.v and R.sub.u are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof;
[0273] Ar.sub.6 is, at each occurrence identically or differently, selected from substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms or a combination thereof; and
[0274] adjacent substituents R.sub.v and R.sub.u can be optionally joined to form a ring.
[0275] In this embodiment, the expression that “adjacent substituents R.sub.v and R.sub.u can be optionally joined to form a ring” is intended to mean that any one or more of groups of adjacent substituents, such as two substituents R.sub.v, two substituents R.sub.u and substituents R.sub.v and R.sub.u, can be joined to form a ring. Obviously, it is possible that none of these substituents are joined to form a ring.
[0276] According to an embodiment of the present disclosure, in the electroluminescent device, the second host compound has a structure represented by one of Formula 5-a to Formula 5-j:
##STR00043## ##STR00044## ##STR00045##
[0277] wherein
[0278] L.sub.x is, at each occurrence identically or differently, selected from a single bond, substituted or unsubstituted alkylene having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkylene having 3 to 20 carbon atoms, substituted or unsubstituted arylene having 6 to 20 carbon atoms, substituted or unsubstituted heteroarylene having 3 to 20 carbon atoms or a combination thereof;
[0279] V is, at each occurrence identically or differently, selected from CR.sub.v or N;
[0280] U is, at each occurrence identically or differently, selected from CR.sub.u or N;
[0281] R.sub.v and R.sub.u are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof;
[0282] Ar.sub.6 is, at each occurrence identically or differently, selected from substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms or a combination thereof; and
[0283] adjacent substituents R.sub.v and R.sub.u can be optionally joined to form a ring.
[0284] According to an embodiment of the present disclosure, the second host compound is selected from the group consisting of X-1 to X-150, wherein the specific structures of X-1 to X-150 are referred to claim 26.
[0285] According to an embodiment of the present disclosure, in the electroluminescent device, the metal complex is doped in the first host compound and the second host compound, and the weight of the metal complex accounts for 1% to 30% of the total weight of the light-emitting layer.
[0286] According to an embodiment of the present disclosure, in the electroluminescent device, the metal complex is doped in the first host compound and the second host compound, and the weight of the metal complex accounts for 3% to 13% of the total weight of the light-emitting layer.
[0287] According to another embodiment of the present disclosure, disclosed is a compound combination comprising the metal complex in any one of the preceding embodiments.
[0288] Combination with Other Materials
[0289] The materials described in the present disclosure for a particular layer in an organic light-emitting device can be used in combination with various other materials present in the device. The combinations of these materials are described in more detail in U.S. Pat. App. No. 20160359122 at paragraphs 0132-0161, which is incorporated by reference herein in its entirety. The materials described or referred to the disclosure are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.
[0290] The materials described herein as useful for a particular layer in an organic light-emitting device may be used in combination with a variety of other materials present in the device. For example, dopants disclosed herein may be used in combination with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes and other layers that may be present. The combination of these materials is described in detail in paragraphs 0080-0101 of U.S. Pat. App. No. 20150349273, which is incorporated by reference herein in its entirety. The materials described or referred to the disclosure are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.
[0291] In the embodiments of material synthesis, all reactions were performed under nitrogen protection unless otherwise stated. All reaction solvents were anhydrous and used as received from commercial sources. Synthetic products were structurally confirmed and tested for properties using one or more conventional equipment in the art (including, but not limited to, nuclear magnetic resonance instrument produced by BRUKER, liquid chromatograph produced by SHIMADZU, liquid chromatograph-mass spectrometry produced by SHIMADZU, gas chromatograph-mass spectrometry produced by SHIMADZU, differential Scanning calorimeters produced by SHIMADZU, fluorescence spectrophotometer produced by SHANGHAI LENGGUANG TECH., electrochemical workstation produced by WUHAN CORRTEST, and sublimation apparatus produced by ANHUI BEQ, etc.) by methods well known to the persons skilled in the art. In the embodiments of the device, the characteristics of the device were also tested using conventional equipment in the art (including, but not limited to, evaporator produced by ANGSTROM ENGINEERING, optical testing system produced by SUZHOU FATAR, life testing system produced by SUZHOU FATAR, and ellipsometer produced by BEIJING ELLITOP, etc.) by methods well known to the persons skilled in the art. As the persons skilled in the art are aware of the above-mentioned equipment use, test methods and other related contents, the inherent data of the sample can be obtained with certainty and without influence, so the above related contents are not further described in this patent.
[0292] Material Synthesis Example
[0293] The method for preparing a compound in the present disclosure is not limited herein. Typically, the following compounds are used as examples without limitations, and synthesis routes and preparation methods thereof are described below.
Synthesis Example 1: Synthesis of Metal Complex 1493
[0294] Step 1:
##STR00046##
[0295] 5-t-butyl-2-phenylpyridine (13.2 g, 62.9 mmol), iridium trichloride trihydrate (5.5 g, 15.7 mmol), 300 mL of 2-ethoxyethanol and 100 mL of water were sequentially added to a dry 500 mL round-bottom flask, purged with nitrogen three times, and heated and stirred for 24 h at 130° C. under nitrogen protection. The solution was cooled, filtered, washed three times with methanol and n-hexane respectively, and pumped to dryness to obtain 9.7 g of Intermediate 1 (with a yield of 97%).
[0296] Step 2:
##STR00047##
[0297] Intermediate 1 (9.7 g, 7.7 mmol), 250 mL of anhydrous dichloromethane, 10 mL of methanol and silver trifluoromethanesulfonate (4.3 g, 16.7 mmol) were sequentially added to a dry 500 mL round-bottom flask, purged with nitrogen three times, and stirred overnight at room temperature under nitrogen protection. The solution was filtered through Celite and washed twice with dichloromethane. The organic phases below were collected and concentrated under reduced pressure to obtain 13.2 g of Intermediate 2 as a yellow solid (with a yield of 93%).
[0298] Step 3:
##STR00048##
[0299] Intermediate 2 (1.4 g, 1.7 mmol), Intermediate 3 (1.0 g, 2.3 mmol) and 50 mL of ethanol and 50 mL of N,N-dimethylformamide were sequentially added to a dry 250 mL round-bottom flask, purged with nitrogen three times, and heated at 80° C. for 72 h under nitrogen protection. The reaction was cooled, filtered through Celite, and washed twice with methanol and n-hexane respectively. Yellow solids on the Celite were dissolved in dichloromethane. The organic phases were collected, concentrated under reduced pressure, and purified through column chromatography to obtain Metal Complex 1493 as a yellow solid (0.5 g with a yield of 28.4%). The product was confirmed as the target product with a molecular weight of 1043.4.
Synthesis Example 2: Synthesis of Metal Complex 1509
[0300] ##STR00049##
[0301] Intermediate 2 (1.8 g, 2.2 mmol), Intermediate 4 (1.0 g, 2.4 mmol), 50 mL of 2-ethoxyethanol and 50 mL of N,N-dimethylformamide were sequentially added to a dry 250 mL round-bottom flask, purged with nitrogen three times, and heated at 100° C. for 72 h under nitrogen protection. The reaction was cooled, filtered through Celite, and washed twice with methanol and n-hexane respectively. Yellow solids on the Celite were dissolved in dichloromethane. The organic phases were collected, concentrated under reduced pressure, and purified through column chromatography to obtain Metal Complex 1509 as a yellow solid (0.41 g with a yield of 18.4%). The product was confirmed as the target product with a molecular weight of 1030.4.
Synthesis Example 3: Synthesis of Metal Complex 1517
[0302] ##STR00050##
[0303] Intermediate 2 (1.8 g, 2.2 mmol), Intermediate 5 (1.3 g, 2.9 mmol), 50 mL of 2-ethoxyethanol and 50 mL of N,N-dimethylformamide were sequentially added to a dry 250 mL round-bottom flask, purged with nitrogen three times, and heated at 100° C. for 72 h under nitrogen protection. The reaction was cooled, filtered through Celite, and washed twice with methanol and n-hexane respectively. Yellow solids on the Celite were dissolved in dichloromethane. The organic phases were collected, concentrated under reduced pressure, and purified through column chromatography to obtain Metal Complex 1517 as a yellow solid (0.83 g with a yield of 35.4%). The product was confirmed as the target product with a molecular weight of 1068.4.
Synthesis Example 4: Synthesis of Metal Complex 1541
[0304] ##STR00051##
[0305] Intermediate 2 (2.5 g, 3.0 mmol), Intermediate 6 (1.8 g, 4.0 mmol), 50 mL of 2-ethoxyethanol and 50 mL of N,N-dimethylformamide were sequentially added to a dry 250 mL round-bottom flask, purged with nitrogen three times, and heated at 100° C. for 72 h under nitrogen protection. The reaction was cooled, filtered through Celite, and washed twice with methanol and n-hexane respectively. Yellow solids on the Celite were dissolved in dichloromethane. The organic phases were collected, concentrated under reduced pressure, and purified through column chromatography to obtain Metal Complex 1541 as a yellow solid (1.14 g with a yield of 35.8%). The product was confirmed as the target product with a molecular weight of 1061.4.
Synthesis Example 5: Synthesis of Metal Complex 113
[0306] Step 1:
##STR00052##
[0307] 5-methyl-2-phenylpyridine (10.0 g, 59.2 mmol), iridium trichloride trihydrate (5.0 g, 14.2 mmol), 300 mL of 2-ethoxyethanol and 100 mL of water were sequentially added to a dry 500 mL round-bottom flask, purged with nitrogen three times, and heated and stirred for 24 h at 130° C. under nitrogen protection. The solution was cooled, filtered, washed three times with methanol and n-hexane respectively, and pumped to dryness to obtain 7.5 g of Intermediate 7 as a yellow solid (with a yield of 97%).
[0308] Step 2:
##STR00053##
[0309] Intermediate 7 (7.5 g, 6.8 mmol), 250 mL of anhydrous dichloromethane, 10 mL of methanol and silver trifluoromethanesulfonate (3.8 g, 14.8 mmol) were sequentially added to a dry 500 mL round-bottom flask, purged with nitrogen three times, and stirred overnight at room temperature under nitrogen protection. The solution was filtered through Celite and washed twice with dichloromethane. The organic phases below were collected and concentrated under reduced pressure to obtain 9.2 g of Intermediate 8 (with a yield of 93%).
[0310] Step 3:
##STR00054##
[0311] Intermediate 8 (2.0 g, 2.7 mmol), Intermediate 9 (1.7 g, 4.1 mmol), 50 mL of 2-ethoxyethanol and 50 mL of N,N-dimethylformamide were sequentially added to a dry 250 mL round-bottom flask, purged with nitrogen three times, and heated at 100° C. for 96 h under nitrogen protection. The reaction was cooled, filtered through Celite, and washed twice with methanol and n-hexane respectively. Yellow solids on the Celite were dissolved in dichloromethane. The organic phases were collected, concentrated under reduced pressure, and purified through column chromatography to obtain Metal Complex 113 as a yellow solid (0.8 g with a yield of 31.4%). The product was confirmed as the target product with a molecular weight of 942.3.
Synthesis Example 6: Synthesis of Metal Complex 123
[0312] ##STR00055##
[0313] Intermediate 8 (1.47 g, 1.9 mmol), Intermediate 10 (1.0 g, 2.2 mmol), 50 mL of 2-ethoxyethanol and 50 mL of N,N-dimethylformamide were sequentially added to a dry 250 mL round-bottom flask, purged with nitrogen three times, and heated at 100° C. for 120 h under nitrogen protection. The reaction was cooled, filtered through Celite, and washed twice with methanol and n-hexane respectively. Yellow solids on the Celite were dissolved in dichloromethane. The organic phases were collected, concentrated under reduced pressure, and purified through column chromatography to obtain Metal Complex 123 as a yellow solid (0.71 g with a yield of 37.9%). The product was confirmed as the target product with a molecular weight of 984.2.
[0314] Those skilled in the art will appreciate that the above preparation methods are merely exemplary. Those skilled in the art can obtain other compound structures of the present disclosure through the modifications of the preparation methods.
Device Example 1
[0315] First, a glass substrate having an indium tin oxide (ITO) anode with a thickness of 80 nm was cleaned and then treated with oxygen plasma and UV ozone. After the treatment, the substrate was dried in a glovebox to remove moisture. Then, the substrate was mounted on a substrate holder and placed in a vacuum chamber. Organic layers specified below were sequentially deposited through vacuum thermal evaporation on the ITO anode at a rate of 0.2 to 2 Angstroms per second and a vacuum degree of about 10.sup.−8 torr. Compound HI was used as a hole injection layer (HIL). Compound HT was used as a hole transporting layer (HTL). Compound H1 was used as an electron blocking layer (EBL). Metal Complex 1493 of the present disclosure was doped in Compound H1 and Compound H2 as a dopant, and the resulting mixture was deposited for use as an emissive layer (EML). On the EML, Compound Di was used as a hole blocking layer (BL). On the HBL, Compound ET and 8-hydroxyquinolinolato-lithium (Liq) were co-deposited for use as an electron transporting layer (ETL). Finally, 8-hydroxyquinolinolato-lithium (Liq) was deposited as an electron injection layer with a thickness of 1 nm and Al was deposited as a cathode with a thickness of 120 nm. The device was transferred back to the glovebox and encapsulated with a glass lid to complete the device.
Device Comparative Example 1
[0316] The implementation in Device Comparative Example 1 was the same as that in Device Example 1, except that in the EML, Metal Complex 1493 of the present disclosure was replaced with Compound GD1.
Device Comparative Example 2
[0317] The implementation in Device Comparative Example 2 was the same as that in Device Example 1, except that in the EML, Metal Complex 1493 of the present disclosure was replaced with Compound GD2.
[0318] Detailed structures and thicknesses of layers of the devices are shown in the following table. A layer using more than one material is obtained by doping different compounds at their weight ratio as recorded.
TABLE-US-00001 TABLE 1 Device structures of Example 1 and Comparative Examples 1 and 2 Device ID HIL HTL EBL EML HBL ETL Example 1 Compound Compound Compound Compound Compound Compound HI HT H1 H1:Compound HB ET:Liq (100 Å) (350 Å) (50 Å) H2:Metal (50 Å) (40:60) Complex (350 Å) 1493(63:31:6) (400 Å) Comparative Compound Compound Compound Compound Compound Compound Example 1 HI HT H1 H1:Compound HB ET:Liq (100 Å) (350 Å) (50 Å) H2:GD1 (50 Å) (40:60) (63:31:6) (350 Å) (400 Å) Comparative Compound Compound Compound Compound Compound Compound Example 2 HI HT H1 H1:Compound HB ET:Liq (100 Å) (350 Å) (50 Å) H2:GD2 (50 Å) (40:60) (63:31:6) (350 Å) (400 Å)
[0319] The structures of the materials used in the devices are shown as follows:
##STR00056## ##STR00057## ##STR00058##
[0320] Current-voltage-luminance (IVL) characteristics of the devices were measured. The CIE data, maximum emission wavelength λ.sub.max, voltage (V), current efficiency (CE), power efficiency (PE) and external quantum efficiency (EQE) of each device were measured at 1000 cd/m.sup.2. The data was recorded and shown in Table 2.
TABLE-US-00002 TABLE 2 Device data of Example 1 and Comparative Examples 1 and 2 λ.sub.max Voltage CE PE EQE Device ID CIE (x, y) (nm) (V) (cd/A) (lm/W) (%) Example 1 (0.357, 0.620) 531 2.94 102 109 26.47 Comparative (0.353, 0.623) 531 3.11 94 95 24.37 Example 1 Comparative (0.368, 0.614) 534 2.98 89 94 23.11 Example 2
[0321] Discussion:
[0322] Table 2 shows the device performance of the metal complex of the present disclosure and the comparative compounds. Compared with Comparative Example 1, Example 1, where the metal complex has a substitution of a fused ring group A at a particular position of the ligand L.sub.a, has basically the same color coordinate and maximum emission wavelength, the voltage reduced by 0.17 V, the CE improved by 8.51%, the PE improved by 14.74%, and the EQE improved by 8.61%. As can be seen from the data, after a particular position of the ligand L.sub.a is substituted by a fused ring group, the device example has a reduced device voltage and improved efficiency compared with the comparative example with a substitution including no fused ring group. The metal complex has significantly better overall device performance than the metal complex in the comparative example and can significantly improve the overall performance of the device.
[0323] Compared with Comparative Example 2, Example 1, where the metal complex has the substitution of the fused ring group A at a different position of the ligand L.sub.a, has basically the same color coordinate, the slightly reduced voltage, the maximum emission wavelength blue-shifted by 3 nm, the CE improved by 14.61%, the PE improved by 15.96%, and the EQE improved by 14.54%. As can be seen from the data, the metal complex having the substitution of the fused ring group A at the particular position of the ligand L.sub.a, which is disclosed in the present disclosure, has significantly improved efficiency and has significantly better overall device performance than the metal complex in the comparative example.
[0324] The above data indicates that the metal complex having the substitution of the fused ring group A at the particular position of the ligand L.sub.a in the present disclosure has significantly better device performance than the metal complexes in the comparative examples and can significantly improve the overall performance of the device.
Device Example 2
[0325] The implementation in Device Example 2 was the same as that in Device Example 1, except that in the EML, Metal Complex 1493 of the present disclosure was replaced with Metal Complex 113 of the present disclosure.
Device Example 3
[0326] The implementation in Device Example 3 was the same as that in Device Example 1, except that in the EML, Metal Complex 1493 of the present disclosure was replaced with Metal Complex 123 of the present disclosure.
Device Example 4
[0327] The implementation in Device Example 4 was the same as that in Device Example 1, except that in the EML, Metal Complex 1493 of the present disclosure was replaced with Metal Complex 1517 of the present disclosure.
Device Example 5
[0328] The implementation in Device Example 5 was the same as that in Device Example 1, except that in the EML, Metal Complex 1493 of the present disclosure was replaced with Metal Complex 1541 of the present disclosure.
Device Comparative Example 3
[0329] The implementation in Device Comparative Example 3 was the same as that in Device Example 1, except that in the EML, Metal Complex 1493 of the present disclosure was replaced with Compound GD3.
Device Comparative Example 4
[0330] The implementation in Device Comparative Example 4 was the same as that in Device Example 1, except that in the EML, Metal Complex 1493 of the present disclosure was replaced with Compound GD4.
Device Comparative Example 5
[0331] The implementation in Device Comparative Example 5 was the same as that in Device Example 1, except that in the EML, Metal Complex 1493 of the present disclosure was replaced with Compound GD5.
[0332] Detailed structures and thicknesses of layers of the devices are shown in the following table. A layer using more than one material is obtained by doping different compounds at their weight ratio as recorded.
TABLE-US-00003 TABLE 3 Device structures of Examples 2 to 5 and Comparative Examples 3 to 5 Device ID HIL HTL EBL EML HBL ETL Example 2 Compound Compound Compound Compound Compound Compound HI HT H1 H1:Compound HB ET:Liq (100 Å) (350 Å) (50 Å) H2:Metal (50 Å) (40:60) Complex 113 (350 Å) (63:31:6) (400 Å) Example 3 Compound Compound Compound Compound Compound Compound HI HT H1 H1:Compound HB ET:Liq (100 Å) (350 Å) (50 Å) H2:Metal (50 Å) (40:60) Complex 123 (350 Å) (63:31:6) (400 Å) Example 4 Compound Compound Compound Compound Compound Compound HI HT H1 H1:Compound HB ET:Liq (100 Å) (350 Å) (50 Å) H2:Metal (50 Å) (40:60) Complex 1517 (350 Å) (63:31:6) (400 Å) Example 5 Compound Compound Compound Compound Compound Compound HI HT H1 H1:Compound HB ET:Liq (100 Å) (350 Å) (50 Å) H2:Metal (50 Å) (40:60) Complex 1541 (350 Å) (63:31:6) (400 Å) Comparative Compound Compound Compound Compound Compound Compound Example 3 HI HT H1 H1:Compound HB ET:Liq (100 Å) (350 Å) (50 Å) H2:Compound (50 Å) (40:60) GD3 (63:31:6) (350 Å) (400 Å) Comparative Compound Compound Compound Compound Compound Compound Example 4 HI HT H1 H1:Compound HB ET:Liq (100 Å) (350 Å) (50 Å) H2:Compound (50 Å) (40:60) GD4 (63:31:6) (350 Å) (400 Å) Comparative Compound Compound Compound Compound Compound Compound Example 5 HI HT H1 H1:Compound HB ET:Liq (100 Å) (350 Å) (50 Å) H2:Compound (50 Å) (40:60) GD5 (63:31:6) (350 Å) (400 Å)
[0333] The structures of the new materials used in the devices are shown as follows:
##STR00059## ##STR00060##
[0334] IVL characteristics of the devices were measured. The CIE data, maximum emission wavelength X.sub.m, voltage (V), current efficiency (CE), power efficiency (PE) and external quantum efficiency (EQE) of each device were measured at 1000 cd/m.sup.2. The data was recorded and shown in Table 4.
TABLE-US-00004 TABLE 4 Device data of Examples 2 to 5 and Comparative Examples 3 to 5 λ.sub.max Voltage CE PE EQE Device ID CIE (x, y) (nm) (V) (cd/A) (lm/W) (%) Example 2 (0.341, 0.635) 530 2.63 109 131 28.11 Example 3 (0.343, 0.633) 530 2.62 109 131 28.03 Example 4 (0.348, 0.630) 531 2.70 109 126 27.54 Example 5 (0.359, 0.619) 532 2.85 101 112 26.35 Comparative (0.342, 0.634) 529 2.68 105 123 26.56 Example 3 Comparative (0.342, 0.635) 531 2.70 104 121 26.21 Example 4 Comparative (0.352, 0.624) 530 3.06 96 98 24.75 Example 5
[0335] Discussion:
[0336] Table 4 shows the device performance of the metal complexes of the present disclosure and the comparative compounds. Compared with Comparative Example 3, Example 2 and Example 3, where the ligand L.sub.a of the metal complex have both a cyano substituent and a substitution of a fused ring group A at a particular position, have basically the same color coordinates and maximum emission wavelengths, the slightly reduced voltages, the CE improved by 3.81%, the PE improved by 6.50%, and the EQE improved by 5.84% and 5.53% respectively. Based on the very good performance of Comparative Example 3, such performance improvements of the above examples are very rare.
[0337] Similarly, compared with Comparative Example 4, Example 4, where the ligand L.sub.a of the metal complex has both a cyano substituent and a substitution of a fused ring group A at a particular position, has basically the same color coordinate, maximum emission wavelength and voltage, the CE improved by 4.81%, the PE improved by 4.13%, and the EQE improved by 5.07%. Based on the very good performance of Comparative Example 4, such performance improvements of the above example are very rare.
[0338] Compared with Comparative Example 5, Example 5, where the ligand L.sub.a of the metal complex has both a fluorine substituent and a substitution of a fused ring group A at a particular position, has basically the same color coordinate, the voltage reduced by 0.21 V, the CE improved by 5.210%, the PE improved by 14.29%, and the EQE improved by 6.46%.
[0339] To sum up, the metal complex of the present disclosure having a substitution of a fused ring group A at a particular position of the ligand L.sub.a, when a substitution is further included in the ligand L.sub.a, also has significantly better overall device performance than the metal complexes in the comparative examples and can significantly improve the overall performance of the device.
[0340] As can be seen from the discussion of the above examples and comparative examples, the metal complex of the present disclosure having a substitution of a particular fused ring A at a particular position of the ligand L.sub.a may be used as a light-emitting material in a light-emitting layer of an electroluminescent device and can significantly improve the overall performance of the device.
[0341] It should be understood that various embodiments described herein are merely examples and not intended to limit the scope of the present disclosure. Therefore, it is apparent to the persons skilled in the art that the present disclosure as claimed may include variations from specific embodiments and preferred embodiments described herein. Many of materials and structures described herein may be substituted with other materials and structures without departing from the spirit of the present disclosure. It should be understood that various theories as to why the present disclosure works are not intended to be limitative.