ORGANIC ELECTROLUMINESCENT MATERIAL AND DEVICE THEREOF
20230047519 · 2023-02-16
Assignee
Inventors
- Zheng Wang (Beijing, CN)
- Hongbo Li (Beijing, CN)
- Ming Sang (Beijing, CN)
- Zhen Wang (Beijing, CN)
- Wei Cai (Beijing, CN)
- Chi Yuen Raymond Kwong (Beijing, CN)
- Chuanjun Xia (Beijing, CN)
Cpc classification
H10K85/6574
ELECTRICITY
H10K85/341
ELECTRICITY
H10K85/6572
ELECTRICITY
H10K85/6576
ELECTRICITY
International classification
Abstract
Provided are an organic electroluminescent material and a device comprising the same. The organic electroluminescent material is a metal complex comprising a ligand L.sub.a having a structure of Formula 1A and a ligand L.sub.b having a structure of Formula 1B. Such new compounds each have a lower evaporation temperature, which is conducive to industrial application of the material and can reduce energy consumption in industrialization. Such metal complexes are used as a light-emitting material in an electroluminescent device. When applied to the electroluminescent device, such metal complexes can provide very excellent device performance, especially an improved device lifetime. Further provided are an organic electroluminescent device comprising the metal complex and a compound composition comprising the metal complex.
Claims
1. A metal complex having a general formula of M(L.sub.a).sub.m(L.sub.b).sub.n(L.sub.c).sub.q; wherein 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.a, L.sub.b and L.sub.c are the same or different; wherein L.sub.a, L.sub.b and L.sub.c can be optionally joined to form a multidentate ligand; the metal M is selected from a metal with a relative atomic mass greater than 40; and m is selected from 1 or 2, n is selected from 1 or 2, q is selected from 0 or 1, and m+n+q equals an oxidation state of M; when m is 2, two L.sub.a are identical or different; when n is 2, two L.sub.b are identical or different; L.sub.a has, at each occurrence identically or differently, a structure represented by Formula 1A and L.sub.b has, at each occurrence identically or differently, a structure represented by Formula 1B: ##STR00054## wherein the ring Cy1 is, at each occurrence identically or differently, selected from a heteroaromatic ring having 5 to 6 ring atoms; the ring Cy2 is, at each occurrence identically or differently, selected from a benzene ring or a heteroaromatic ring having 5 to 6 ring atoms; Ar 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; a, b, c, d and e are, at each occurrence identically or differently, selected from 0 or 1, and at least one of a, b, c and d is selected from 1; Z is, at each occurrence identically or differently, selected from O or X═X; X is, at each occurrence identically or differently, selected from N or CR′; U.sub.1 to U.sub.6 are, at each occurrence identically or differently, selected from CR.sub.u or N; R″ is, at each occurrence identically or differently, selected from mono-substitution, multiple substitutions or non-substitution; R′, R″ 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; “*” represents a position where the ring Cy1 or the ring Cy2 is joined; in Formula 1A, adjacent substituents R.sub.u can be optionally joined to form a ring; in Formula 1B, adjacent substituents R′ and R″ can be optionally joined to form a ring; and R.sub.1 is, at each occurrence identically or differently, selected from the group consisting of: substituted or unsubstituted alkyl having 4 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 4 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 4 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 4 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 4 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 4 to 20 carbon atoms, substituted or unsubstituted alkynyl having 4 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 4 to 30 carbon atoms and combinations thereof; R.sub.2 has a structure represented by Formula 2: ##STR00055## wherein the number of carbon atoms in R.sub.2 is greater than or equal to 4; R.sub.3, R.sub.4 and R.sub.5 are, at each occurrence identically or differently, selected from the group consisting of: 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; ##STR00056## represents a position where Formula 2 is joined to Formula 1A; two adjacent substituents of R.sub.3, R.sub.4 and R.sub.5 can be optionally joined to form a ring; and L.sub.c is a monoanionic bidentate ligand.
2. The metal complex according to claim 1, wherein the ring Cy1 is, at each occurrence identically or differently, selected from any structure of the group consisting of the following: ##STR00057## and/or the ring Cy2 is, at each occurrence identically or differently, selected from any structure of the group consisting of the following: ##STR00058## wherein “#” represents a position where the ring Cy1/Cy2 is joined to the Metal M, and ##STR00059## represents a position where the ring Cy1 is joined to the ring Cy2; and definitions of substituents R″ and Ar on the ring Cy1 and that the structure is fused at the position “*” are the same as those in claim 1, and definitions of substituents R″ and Ar on the ring Cy2 and that the structure is fused at the position “*” are the same as those in claim 1.
3. The metal complex according to claim 1, wherein L.sub.b has, at each occurrence identically or differently, a structure represented by any one of Formulas 1Ba to 1Bm: ##STR00060## ##STR00061## ##STR00062## wherein X.sub.1 to X.sub.8 are, at each occurrence identically or differently, selected from CR.sub.x or N; Y.sub.1 to Y.sub.12 are, at each occurrence identically or differently, selected from CR.sub.y or N; Ar 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; R.sub.x and R.sub.y 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.sub.x and R.sub.y can be optionally joined to form a ring; and preferably, L.sub.b has, at each occurrence identically or differently, a structure represented by any one of Formulas 1Ba to 1Bi.
4. The metal complex according to claim 1, wherein R.sub.1 is, at each occurrence identically or differently, selected from the group consisting of: substituted or unsubstituted alkyl having 4 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 4 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 4 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 4 to 20 ring atoms and combinations thereof; and preferably, R.sub.1 is, at each occurrence identically or differently, selected from the group consisting of: substituted or unsubstituted alkyl having 4 to 10 carbon atoms, substituted or unsubstituted cycloalkyl having 4 to 10 ring carbon atoms and combinations thereof.
5. The metal complex according to claim 1, wherein 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; and preferably, M is, at each occurrence identically or differently, selected from Pt or Ir.
6. The metal complex according to claim 1, wherein R.sub.1 has a structure represented by Formula 2.
7. The metal complex according to claim 1, wherein R.sub.3, R.sub.4 and R.sub.5 are, at each occurrence identically or differently, selected from the group consisting of: 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 ring 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 alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms or substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms; preferably, R.sub.3, R.sub.4 and R.sub.5 are, at each occurrence identically or differently, selected from the group consisting of: 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 and combinations thereof; and more preferably, R.sub.3, R.sub.4 and R.sub.5 are, at each occurrence identically or differently, selected from the group consisting of: halogen, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms and combinations thereof.
8. The metal complex according to claim 1, wherein the structure represented by Formula 2 represents, at each occurrence identically or differently, any one of the following structures: ##STR00063## ##STR00064## wherein “*” represents a position where the structure is joined to Formula 1A; and optionally, hydrogen atoms in the above structures can be partially or fully substituted with deuterium atoms.
9. The metal complex according to claim 1, wherein the metal complex has a structure of a general formula of Ir(L.sub.a).sub.m(L.sub.b).sub.3-m which is represented by Formula 3, Formula 4 or Formula 5: ##STR00065## wherein m is selected from 1 or 2; when m=1, two L.sub.b are identical or different; when m=2, two L.sub.a are identical or different; X.sub.3 to X.sub.8 are, at each occurrence identically or differently, selected from CR.sub.x or N; Y.sub.1 to Y.sub.8 are, at each occurrence identically or differently, selected from C, CR.sub.y or N; U.sub.1 to U.sub.6 are, at each occurrence identically or differently, selected from CR.sub.u or N; Ar 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; R.sub.x, R.sub.y 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 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 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; R.sub.3, R.sub.4 and R.sub.5 are, at each occurrence identically or differently, selected from the group consisting of: 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 alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms or substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms; adjacent substituents R.sub.x and R.sub.y can be optionally joined to form a ring; and two adjacent substituents of R.sub.3, R.sub.4 and R.sub.5 can be optionally joined to form a ring.
10. The metal complex according to claim 3, 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 arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, a cyano group, a hydroxyl group, a sulfanyl group and combinations thereof; and preferably, 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 heteroalkyl 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, a cyano group and combinations thereof.
11. The metal complex according to claim 3, wherein at least one of X.sub.3 to X.sub.8 is selected from CR.sub.x, and R.sub.x is selected from cyano or fluorine; preferably, at least one of X.sub.5 to X.sub.8 is selected from CR.sub.x, and R.sub.x is selected from cyano or fluorine; and more preferably, X.sub.7 or X.sub.8 is selected from CR.sub.x, and R.sub.x is selected from cyano or fluorine.
12. The metal complex according to claim 3, wherein at least two of X.sub.3 to X.sub.8 are selected from CR.sub.x, wherein one R.sub.x is selected from cyano or fluorine, and at least another one R.sub.x 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 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 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; preferably, at least two of X.sub.5 to X.sub.8 are selected from CR.sub.x, wherein one R.sub.x is selected from cyano or fluorine, and at least another one R.sub.x 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, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, a cyano group, a hydroxyl group, a sulfanyl group and combinations thereof; and more preferably, X.sub.7 and X.sub.8 are selected from CR.sub.x, wherein one R.sub.x is cyano or fluorine, and another one R.sub.x 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.
13. The metal complex according to claim 9, wherein U.sub.1 to U.sub.6 are, at each occurrence identically or differently, selected from CR.sub.u, and/or Y.sub.1 to Y.sub.4 are, at each occurrence identically or differently, selected from CR.sub.y, and/or X.sub.3 to X.sub.8 are, at each occurrence identically or differently, selected from CR.sub.x.
14. The metal complex according to claim 9, wherein R.sub.u and R.sub.y 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 aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms and combinations thereof; preferably, R.sub.u and R.sub.y are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, substituted or unsubstituted alkyl having 1 to 10 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 10 ring carbon atoms, substituted or unsubstituted aryl having 6 to 10 carbon atoms and combinations thereof; and more preferably, R.sub.u and R.sub.y are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, substituted or unsubstituted alkyl having 1 to 10 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 10 ring carbon atoms and combinations thereof.
15. The metal complex according to claim 9, wherein at least one of U.sub.1 to U.sub.3 is selected from N, and/or at least one of U.sub.4 to U.sub.6 is selected from N, and/or at least one of Y.sub.1 to Y.sub.4 is selected from N, and/or at least one of X.sub.3 to X.sub.8 is selected from N.
16. The metal complex according to claim 1, wherein Ar is, at each occurrence identically or differently, selected from substituted or unsubstituted aryl having 6 to 24 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 24 carbon atoms or a combination thereof; preferably, Ar is, at each occurrence identically or differently, selected from substituted or unsubstituted aryl having 6 to 12 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 12 carbon atoms or a combination thereof; and more preferably, Ar is, at each occurrence identically or differently, selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted pyridyl or a combination thereof.
17. The metal complex according to claim 1, wherein L.sub.a is, at each occurrence identically or differently, selected from the group consisting of the following: ##STR00066## ##STR00067## ##STR00068## ##STR00069## ##STR00070## ##STR00071## ##STR00072## ##STR00073## ##STR00074## ##STR00075## ##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## ##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## wherein optionally, hydrogen atoms in L.sub.a1-1 to L.sub.a1-231, L.sub.a2-1 to L.sub.a2-161 and L.sub.a3-1 to L.sub.a3-130 can be partially or fully substituted with deuterium atoms.
18. The metal complex according to claim 1, wherein L.sub.b is, at each occurrence identically or differently, selected from the group consisting of the following: ##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## wherein optionally, hydrogen atoms in L.sub.b1-1 to L.sub.b1-355, L.sub.b2-1 to L.sub.b2-261 and L.sub.b34 to L.sub.b3-650 can be partially or fully substituted with deuterium atoms.
19. The metal complex according to claim 18, wherein the metal complex has a structure of Ir(L.sub.a)(L.sub.b)(L.sub.c), wherein L.sub.a is selected from the group consisting of L.sub.a1-1 to L.sub.a1-231, L.sub.a2-1 to L.sub.a2-161, L.sub.a3-1 to L.sub.a3-130, L.sub.b is selected from the group consisting of L.sub.b1-1 to L.sub.b1-355, L.sub.b24 to L.sub.b2-261, L.sub.b3-1 to L.sub.b3-650, and L.sub.c is, at each occurrence identically or differently, selected from the group consisting of the following: ##STR00447## ##STR00448## ##STR00449## ##STR00450## ##STR00451## ##STR00452## ##STR00453## ##STR00454## ##STR00455## ##STR00456## ##STR00457## ##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##
20. The metal complex according to claim 18, wherein the metal complex has a structure of Ir(La).sub.2Lb, wherein the two L.sub.a are identical or different, L.sub.a is selected from the group consisting of L.sub.a1-1 to L.sub.a1-231, L.sub.a2-1 to L.sub.a2-161 and L.sub.a3-1 to L.sub.a3-130, and L.sub.b is selected from the group consisting of L.sub.b1-1 to L.sub.b1-355, L.sub.b2-1 to L.sub.b2-261 and L.sub.b3-1 to L.sub.b3-650; preferably, the metal complex is selected from the group consisting of Metal Complex 1 to Metal Complex 2128, wherein Metal Complex 1 to Metal Complex 2128 have the structure of Ir(L.sub.a).sub.2L.sub.b, wherein the two L.sub.a are identical and L.sub.a and L.sub.b correspond to structures shown in the following table, respectively: TABLE-US-00007 Metal Metal Complex Complex No. L.sub.a L.sub.b No. L.sub.a L.sub.b 1 L.sub.a1-1 L.sub.b1-1 2 L.sub.a1-1 L.sub.b1-2 3 L.sub.a1-1 L.sub.b1-3 4 L.sub.a1-1 L.sub.b1-4 5 L.sub.a1-1 L.sub.b1-5 6 L.sub.a1-1 L.sub.b1-6 7 L.sub.a1-1 L.sub.b1-7 8 L.sub.a1-1 L.sub.b1-8 9 L.sub.a1-1 L.sub.b1-9 10 L.sub.a1-1 L.sub.b1-10 11 L.sub.a1-1 L.sub.b1-11 12 L.sub.a1-1 L.sub.b1-12 13 L.sub.a1-1 L.sub.b1-13 14 L.sub.a1-1 L.sub.b1-14 15 L.sub.a1-1 L.sub.b1-15 16 L.sub.a1-1 L.sub.b1-16 17 L.sub.a1-1 L.sub.b1-17 18 L.sub.a1-1 L.sub.b1-18 19 L.sub.a1-1 L.sub.b1-19 20 L.sub.a1-1 L.sub.b1-20 21 L.sub.a1-1 L.sub.b1-21 22 L.sub.a1-1 L.sub.b1-22 23 L.sub.a1-1 L.sub.b1-23 24 L.sub.a1-1 L.sub.b1-24 25 L.sub.a1-1 L.sub.b1-25 26 L.sub.a1-1 L.sub.b1-26 27 L.sub.a1-1 L.sub.b1-27 28 L.sub.a1-1 L.sub.b1-28 29 L.sub.a1-1 L.sub.b1-29 30 L.sub.a1-1 L.sub.b1-30 31 L.sub.a1-1 L.sub.b1-45 32 L.sub.a1-1 L.sub.b1-46 33 L.sub.a1-1 L.sub.b1-47 34 L.sub.a1-1 L.sub.b1-48 35 L.sub.a1-1 L.sub.b1-49 36 L.sub.a1-1 L.sub.b1-50 37 L.sub.a1-1 L.sub.b1-51 38 L.sub.a1-1 L.sub.b1-52 39 L.sub.a1-1 L.sub.b1-53 40 L.sub.a1-1 L.sub.b1-54 41 L.sub.a1-1 L.sub.b1-55 42 L.sub.a1-1 L.sub.b1-56 43 L.sub.a1-1 L.sub.b1-57 44 L.sub.a1-1 L.sub.b1-58 45 L.sub.a1-1 L.sub.b1-59 46 L.sub.a1-1 L.sub.b1-60 47 L.sub.a1-1 L.sub.b1-61 48 L.sub.a1-1 L.sub.b1-62 49 L.sub.a1-1 L.sub.b1-63 50 L.sub.a1-1 L.sub.b1-64 51 L.sub.a1-1 L.sub.b1-65 52 L.sub.a1-1 L.sub.b1-66 53 L.sub.a1-1 L.sub.b1-67 54 L.sub.a1-1 L.sub.b1-68 55 L.sub.a1-1 L.sub.b1-69 56 L.sub.a1-1 L.sub.b1-70 57 L.sub.a1-1 L.sub.b1-71 58 L.sub.a1-1 L.sub.b1-72 59 L.sub.a1-1 L.sub.b1-73 60 L.sub.a1-1 L.sub.b1-74 61 L.sub.a1-1 L.sub.b1-75 62 L.sub.a1-1 L.sub.b1-76 63 L.sub.a1-1 L.sub.b1-77 64 L.sub.a1-1 L.sub.b1-78 65 L.sub.a1-1 L.sub.b1-79 66 L.sub.a1-1 L.sub.b1-80 67 L.sub.a1-1 L.sub.b1-81 68 L.sub.a1-1 L.sub.b1-82 69 L.sub.a1-1 L.sub.b1-83 70 L.sub.a1-1 L.sub.b1-84 71 L.sub.a1-1 L.sub.b1-85 72 L.sub.a1-1 L.sub.b1-86 73 L.sub.a1-1 L.sub.b1-87 74 L.sub.a1-1 L.sub.b1-88 75 L.sub.a1-1 L.sub.b1-89 76 L.sub.a1-1 L.sub.b1-90 77 L.sub.a1-1 L.sub.b1-91 78 L.sub.a1-1 L.sub.b1-92 79 L.sub.a1-1 L.sub.b1-120 80 L.sub.a1-1 L.sub.b1-121 81 L.sub.a1-1 L.sub.b1-122 82 L.sub.a1-1 L.sub.b1-123 83 L.sub.a1-1 L.sub.b1-124 84 L.sub.a1-1 L.sub.b1-125 85 L.sub.a1-1 L.sub.b1-126 86 L.sub.a1-1 L.sub.b1-127 87 L.sub.a1-1 L.sub.b1-159 88 L.sub.a1-1 L.sub.b1-160 89 L.sub.a1-1 L.sub.b1-161 90 L.sub.a1-1 L.sub.b1-162 91 L.sub.a1-1 L.sub.b1-282 92 L.sub.a1-1 L.sub.b1-283 93 L.sub.a1-1 L.sub.b1-284 94 L.sub.a1-1 L.sub.b1-285 95 L.sub.a1-1 L.sub.b1-286 96 L.sub.a1-1 L.sub.b1-287 97 L.sub.a1-1 L.sub.b1-288 98 L.sub.a1-1 L.sub.b1-289 99 L.sub.a1-1 L.sub.b1-290 100 L.sub.a1-1 L.sub.b1-291 101 L.sub.a1-1 L.sub.b1-292 102 L.sub.a1-1 L.sub.b1-293 103 L.sub.a1-1 L.sub.b1-294 104 L.sub.a1-1 L.sub.b1-295 105 L.sub.a1-1 L.sub.b1-296 106 L.sub.a1-1 L.sub.b1-297 107 L.sub.a1-1 L.sub.b1-298 108 L.sub.a1-1 L.sub.b1-299 109 L.sub.a1-1 L.sub.b1-300 110 L.sub.a1-1 L.sub.b1-301 111 L.sub.a1-1 L.sub.b1-302 112 L.sub.a1-1 L.sub.b1-303 113 L.sub.a1-1 L.sub.b1-304 114 L.sub.a1-1 L.sub.b1-305 115 L.sub.a1-1 L.sub.b1-306 116 L.sub.a1-1 L.sub.b1-307 117 L.sub.a1-1 L.sub.b1-308 118 L.sub.a1-1 L.sub.b1-309 119 L.sub.a1-1 L.sub.b1-310 120 L.sub.a1-1 L.sub.b1-311 121 L.sub.a1-1 L.sub.b1-312 122 L.sub.a1-1 L.sub.b1-313 123 L.sub.a1-1 L.sub.b1-314 124 L.sub.a1-1 L.sub.b1-315 125 L.sub.a1-1 L.sub.b1-316 126 L.sub.a1-1 L.sub.b1-317 127 L.sub.a1-1 L.sub.b1-318 128 L.sub.a1-1 L.sub.b1-319 129 L.sub.a1-1 L.sub.b1-320 130 L.sub.a1-1 L.sub.b1-321 131 L.sub.a1-1 L.sub.b1-322 132 L.sub.a1-1 L.sub.b1-323 133 L.sub.a1-1 L.sub.b1-342 134 L.sub.a1-1 L.sub.b1-343 135 L.sub.a1-1 L.sub.b1-344 136 L.sub.a1-1 L.sub.b1-344 137 L.sub.a1-1 L.sub.b1-346 138 L.sub.a1-1 L.sub.b1-345 139 L.sub.a1-1 L.sub.b1-348 140 L.sub.a1-1 L.sub.b1-346 141 L.sub.a1-1 L.sub.b1-350 142 L.sub.a1-1 L.sub.b1-347 143 L.sub.a1-1 L.sub.b1-352 144 L.sub.a1-1 L.sub.b1-348 145 L.sub.a1-1 L.sub.b1-354 146 L.sub.a1-1 L.sub.b1-349 147 L.sub.a1-1 L.sub.b2-1 148 L.sub.a1-1 L.sub.b2-2 149 L.sub.a1-1 L.sub.b2-3 150 L.sub.a1-1 L.sub.b2-4 151 L.sub.a1-1 L.sub.b2-5 152 L.sub.a1-1 L.sub.b2-6 153 L.sub.a1-1 L.sub.b2-7 154 L.sub.a1-1 L.sub.b2-8 155 L.sub.a1-1 L.sub.b2-9 156 L.sub.a1-1 L.sub.b2-10 157 L.sub.a1-1 L.sub.b2-11 158 L.sub.a1-1 L.sub.b2-12 159 L.sub.a1-1 L.sub.b2-22 160 L.sub.a1-1 L.sub.b2-23 161 L.sub.a1-1 L.sub.b2-24 162 L.sub.a1-1 L.sub.b2-25 163 L.sub.a1-1 L.sub.b2-26 164 L.sub.a1-1 L.sub.b2-27 165 L.sub.a1-1 L.sub.b2-28 166 L.sub.a1-1 L.sub.b2-29 167 L.sub.a1-1 L.sub.b2-30 168 L.sub.a1-1 L.sub.b2-31 169 L.sub.a1-1 L.sub.b2-32 170 L.sub.a1-1 L.sub.b2-33 171 L.sub.a1-1 L.sub.b2-34 172 L.sub.a1-1 L.sub.b2-35 173 L.sub.a1-1 L.sub.b2-36 174 L.sub.a1-1 L.sub.b2-37 175 L.sub.a1-1 L.sub.b2-49 176 L.sub.a1-1 L.sub.b2-50 177 L.sub.a1-1 L.sub.b2-51 178 L.sub.a1-1 L.sub.b2-52 179 L.sub.a1-1 L.sub.b2-53 180 L.sub.a1-1 L.sub.b2-54 181 L.sub.a1-1 L.sub.b2-55 182 L.sub.a1-1 L.sub.b2-56 183 L.sub.a1-1 L.sub.b2-57 184 L.sub.a1-1 L.sub.b2-58 185 L.sub.a1-1 L.sub.b2-59 186 L.sub.a1-1 L.sub.b2-60 187 L.sub.a1-1 L.sub.b2-61 188 L.sub.a1-1 L.sub.b2-62 189 L.sub.a1-1 L.sub.b2-63 190 L.sub.a1-1 L.sub.b2-64 191 L.sub.a1-1 L.sub.b2-65 192 L.sub.a1-1 L.sub.b2-66 193 L.sub.a1-1 L.sub.b2-67 194 L.sub.a1-1 L.sub.b2-68 195 L.sub.a1-1 L.sub.b2-69 196 L.sub.a1-1 L.sub.b2-70 197 L.sub.a1-1 L.sub.b2-94 198 L.sub.a1-1 L.sub.b2-95 199 L.sub.a1-1 L.sub.b2-164 200 L.sub.a1-1 L.sub.b2-165 201 L.sub.a1-1 L.sub.b2-166 202 L.sub.a1-1 L.sub.b2-167 203 L.sub.a1-1 L.sub.b2-168 204 L.sub.a1-1 L.sub.b2-169 205 L.sub.a1-1 L.sub.b2-170 206 L.sub.a1-1 L.sub.b2-171 207 L.sub.a1-1 L.sub.b2-172 208 L.sub.a1-1 L.sub.b2-173 209 L.sub.a1-1 L.sub.b2-174 210 L.sub.a1-1 L.sub.b2-175 211 L.sub.a1-1 L.sub.b2-176 212 L.sub.a1-1 L.sub.b2-177 213 L.sub.a1-1 L.sub.b2-178 214 L.sub.a1-1 L.sub.b2-179 215 L.sub.a1-1 L.sub.b2-180 216 L.sub.a1-1 L.sub.b2-181 217 L.sub.a1-1 L.sub.b2-182 218 L.sub.a1-1 L.sub.b2-183 219 L.sub.a1-1 L.sub.b2-184 220 L.sub.a1-1 L.sub.b2-185 221 L.sub.a1-1 L.sub.b2-186 222 L.sub.a1-1 L.sub.b2-187 223 L.sub.a1-1 L.sub.b2-188 224 L.sub.a1-1 L.sub.b2-189 225 L.sub.a1-1 L.sub.b2-190 226 L.sub.a1-1 L.sub.b2-191 227 L.sub.a1-1 L.sub.b2-192 228 L.sub.a1-1 L.sub.b2-193 229 L.sub.a1-1 L.sub.b2-194 230 L.sub.a1-1 L.sub.b2-195 231 L.sub.a1-1 L.sub.b2-196 232 L.sub.a1-1 L.sub.b2-197 233 L.sub.a1-1 L.sub.b2-198 234 L.sub.a1-1 L.sub.b2-199 235 L.sub.a1-1 L.sub.b2-200 236 L.sub.a1-1 L.sub.b2-201 237 L.sub.a1-1 L.sub.b2-202 238 L.sub.a1-1 L.sub.b2-203 239 L.sub.a1-1 L.sub.b2-204 240 L.sub.a1-1 L.sub.b2-205 241 L.sub.a1-1 L.sub.b2-214 242 L.sub.a1-1 L.sub.b2-215 243 L.sub.a1-1 L.sub.b2-216 244 L.sub.a1-1 L.sub.b2-217 245 L.sub.a1-1 L.sub.b2-218 246 L.sub.a1-1 L.sub.b2-219 247 L.sub.a1-1 L.sub.b2-232 248 L.sub.a1-1 L.sub.b2-233 249 L.sub.a1-1 L.sub.b2-234 250 L.sub.a1-1 L.sub.b2-235 251 L.sub.a1-1 L.sub.b2-236 252 L.sub.a1-1 L.sub.b2-237 253 L.sub.a1-1 L.sub.b2-238 254 L.sub.a1-1 L.sub.b2-239 255 L.sub.a1-1 L.sub.b2-240 256 L.sub.a1-1 L.sub.b2-241 257 L.sub.a1-1 L.sub.b2-242 258 L.sub.a1-1 L.sub.b2-243 259 L.sub.a1-1 L.sub.b3-1 260 L.sub.a1-1 L.sub.b3-2 261 L.sub.a1-1 L.sub.b3-3 262 L.sub.a1-1 L.sub.b3-4 263 L.sub.a1-1 L.sub.b3-38 264 L.sub.a1-1 L.sub.b3-39 265 L.sub.a1-1 L.sub.b3-57 266 L.sub.a1-1 L.sub.b3-58 267 L.sub.a1-1 L.sub.b3-59 268 L.sub.a1-1 L.sub.b3-60 269 L.sub.a1-1 L.sub.b3-59 270 L.sub.a1-1 L.sub.b3-60 271 L.sub.a1-1 L.sub.b3-60 272 L.sub.a1-1 L.sub.b3-61 273 L.sub.a1-1 L.sub.b3-61 274 L.sub.a1-1 L.sub.b3-62 275 L.sub.a1-1 L.sub.b3-66 276 L.sub.a1-1 L.sub.b3-67 277 L.sub.a1-1 L.sub.b3-68 278 L.sub.a1-1 L.sub.b3-69 279 L.sub.a1-1 L.sub.b3-80 280 L.sub.a1-1 L.sub.b3-81 281 L.sub.a1-1 L.sub.b3-316 282 L.sub.a1-1 L.sub.b3-317 283 L.sub.a1-1 L.sub.b3-337 284 L.sub.a1-1 L.sub.b3-338 285 L.sub.a1-1 L.sub.b3-380 286 L.sub.a1-1 L.sub.b3-381 287 L.sub.a1-1 L.sub.b3-384 288 L.sub.a1-1 L.sub.b3-386 289 L.sub.a1-1 L.sub.b3-390 290 L.sub.a1-1 L.sub.b3-410 291 L.sub.a1-1 L.sub.b3-422 292 L.sub.a1-1 L.sub.b3-433 293 L.sub.a1-1 L.sub.b3-444 294 L.sub.a1-1 L.sub.b3-450 295 L.sub.a1-1 L.sub.b3-451 296 L.sub.a1-1 L.sub.b3-470 297 L.sub.a1-1 L.sub.b3-479 298 L.sub.a1-1 L.sub.b3-480 299 L.sub.a1-1 L.sub.b3-484 300 L.sub.a1-1 L.sub.b3-490 301 L.sub.a1-1 L.sub.b3-504 302 L.sub.a1-1 L.sub.b3-508 303 L.sub.a1-1 L.sub.b3-509 304 L.sub.a1-1 L.sub.b3-510 305 L.sub.a1-1 L.sub.b3-533 306 L.sub.a1-1 L.sub.b3-550 307 L.sub.a1-1 L.sub.b3-562 308 L.sub.a1-1 L.sub.b3-574 309 L.sub.a1-1 L.sub.b3-578 310 L.sub.a1-1 L.sub.b3-584 311 L.sub.a1-8 L.sub.b1-1 312 L.sub.a1-8 L.sub.b1-2 313 L.sub.a1-8 L.sub.b1-3 314 L.sub.a1-8 L.sub.b1-4 315 L.sub.a1-8 L.sub.b1-5 316 L.sub.a1-8 L.sub.b1-6 317 L.sub.a1-8 L.sub.b1-7 318 L.sub.a1-8 L.sub.b1-8 319 L.sub.a1-8 L.sub.b1-9 320 L.sub.a1-8 L.sub.b1-10 321 L.sub.a1-8 L.sub.b1-11 322 L.sub.a1-8 L.sub.b1-12 323 L.sub.a1-8 L.sub.b1-13 324 L.sub.a1-8 L.sub.b1-14 325 L.sub.a1-8 L.sub.b1-15 326 L.sub.a1-8 L.sub.b1-16 327 L.sub.a1-8 L.sub.b1-17 328 L.sub.a1-8 L.sub.b1-18 329 L.sub.a1-8 L.sub.b1-19 330 L.sub.a1-8 L.sub.b1-20 331 L.sub.a1-8 L.sub.b1-21 332 L.sub.a1-8 L.sub.b1-22 333 L.sub.a1-8 L.sub.b1-23 334 L.sub.a1-8 L.sub.b1-24 335 L.sub.a1-8 L.sub.b1-25 336 L.sub.a1-8 L.sub.b1-26 337 L.sub.a1-8 L.sub.b1-27 338 L.sub.a1-8 L.sub.b1-28 339 L.sub.a1-8 L.sub.b1-29 340 L.sub.a1-8 L.sub.b1-30 341 L.sub.a1-8 L.sub.b1-45 342 L.sub.a1-8 L.sub.b1-46 343 L.sub.a1-8 L.sub.b1-47 344 L.sub.a1-8 L.sub.b1-48 345 L.sub.a1-8 L.sub.b1-49 346 L.sub.a1-8 L.sub.b1-50 347 L.sub.a1-8 L.sub.b1-51 348 L.sub.a1-8 L.sub.b1-52 349 L.sub.a1-8 L.sub.b1-53 350 L.sub.a1-8 L.sub.b1-54 351 L.sub.a1-8 L.sub.b1-55 352 L.sub.a1-8 L.sub.b1-56 353 L.sub.a1-8 L.sub.b1-57 354 L.sub.a1-8 L.sub.b1-58 355 L.sub.a1-8 L.sub.b1-59 356 L.sub.a1-8 L.sub.b1-60 357 L.sub.a1-8 L.sub.b1-61 358 L.sub.a1-8 L.sub.b1-62 359 L.sub.a1-8 L.sub.b1-63 360 L.sub.a1-8 L.sub.b1-64 361 L.sub.a1-8 L.sub.b1-65 362 L.sub.a1-8 L.sub.b1-66 363 L.sub.a1-8 L.sub.b1-67 364 L.sub.a1-8 L.sub.b1-68 365 L.sub.a1-8 L.sub.b1-69 366 L.sub.a1-8 L.sub.b1-70 367 L.sub.a1-8 L.sub.b1-71 368 L.sub.a1-8 L.sub.b1-72 369 L.sub.a1-8 L.sub.b1-73 370 L.sub.a1-8 L.sub.b1-74 371 L.sub.a1-8 L.sub.b1-75 372 L.sub.a1-8 L.sub.b1-76 373 L.sub.a1-8 L.sub.b1-77 374 L.sub.a1-8 L.sub.b1-78 375 L.sub.a1-8 L.sub.b1-79 376 L.sub.a1-8 L.sub.b1-80 377 L.sub.a1-8 L.sub.b1-81 378 L.sub.a1-8 L.sub.b1-82 379 L.sub.a1-8 L.sub.b1-83 380 L.sub.a1-8 L.sub.b1-84 381 L.sub.a1-8 L.sub.b1-85 382 L.sub.a1-8 L.sub.b1-86 383 L.sub.a1-8 L.sub.b1-87 384 L.sub.a1-8 L.sub.b1-88 385 L.sub.a1-8 L.sub.b1-89 386 L.sub.a1-8 L.sub.b1-90 387 L.sub.a1-8 L.sub.b1-91 388 L.sub.a1-8 L.sub.b1-92 389 L.sub.a1-8 L.sub.b1-120 390 L.sub.a1-8 L.sub.b1-121 391 L.sub.a1-8 L.sub.b1-122 392 L.sub.a1-8 L.sub.b1-123 393 L.sub.a1-8 L.sub.b1-124 394 L.sub.a1-8 L.sub.b1-125 395 L.sub.a1-8 L.sub.b1-126 396 L.sub.a1-8 L.sub.b1-127 397 L.sub.a1-8 L.sub.b1-159 398 L.sub.a1-8 L.sub.b1-160 399 L.sub.a1-8 L.sub.b1-161 400 L.sub.a1-8 L.sub.b1-162 401 L.sub.a1-8 L.sub.b1-282 402 L.sub.a1-8 L.sub.b1-283 403 L.sub.a1-8 L.sub.b1-284 404 L.sub.a1-8 L.sub.b1-285 405 L.sub.a1-8 L.sub.b1-286 406 L.sub.a1-8 L.sub.b1-287 407 L.sub.a1-8 L.sub.b1-288 408 L.sub.a1-8 L.sub.b1-289 409 L.sub.a1-8 L.sub.b1-290 410 L.sub.a1-8 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1551 L.sub.a1-149 L.sub.b1-282 1552 L.sub.a1-150 L.sub.b1-282 1553 L.sub.a1-151 L.sub.b1-282 1554 L.sub.a1-152 L.sub.b1-282 1555 L.sub.a1-153 L.sub.b1-282 1556 L.sub.a1-154 L.sub.b1-282 1557 L.sub.a1-155 L.sub.b1-282 1558 L.sub.a1-156 L.sub.b1-282 1559 L.sub.a1-157 L.sub.b1-282 1560 L.sub.a1-158 L.sub.b1-282 1561 L.sub.a1-159 L.sub.b1-282 1562 L.sub.a1-160 L.sub.b1-282 1563 L.sub.a1-161 L.sub.b1-282 1564 L.sub.a1-162 L.sub.b1-282 1565 L.sub.a1-163 L.sub.b1-282 1566 L.sub.a1-164 L.sub.b1-282 1567 L.sub.a1-165 L.sub.b1-282 1568 L.sub.a1-166 L.sub.b1-282 1569 L.sub.a1-167 L.sub.b1-282 1570 L.sub.a1-168 L.sub.b1-282 1571 L.sub.a1-169 L.sub.b1-282 1572 L.sub.a1-170 L.sub.b1-282 1573 L.sub.a1-171 L.sub.b1-282 1574 L.sub.a1-172 L.sub.b1-282 1575 L.sub.a1-173 L.sub.b1-282 1576 L.sub.a1-174 L.sub.b1-282 1577 L.sub.a1-175 L.sub.b1-282 1578 L.sub.a1-176 L.sub.b1-282 1579 L.sub.a1-177 L.sub.b1-282 1580 L.sub.a1-178 L.sub.b1-282 1581 L.sub.a1-179 L.sub.b1-282 1582 L.sub.a1-180 L.sub.b1-282 1583 L.sub.a1-181 L.sub.b1-282 1584 L.sub.a1-182 L.sub.b1-282 1585 L.sub.a1-183 L.sub.b1-282 1586 L.sub.a1-184 L.sub.b1-282 1587 L.sub.a1-185 L.sub.b1-282 1588 L.sub.a1-186 L.sub.b1-282 1589 L.sub.a2-2 L.sub.b1-282 1590 L.sub.a2-3 L.sub.b1-282 1591 L.sub.a2-4 L.sub.b1-282 1592 L.sub.a2-5 L.sub.b1-282 1593 L.sub.a2-6 L.sub.b1-282 1594 L.sub.a2-7 L.sub.b1-282 1595 L.sub.a2-8 L.sub.b1-282 1596 L.sub.a2-9 L.sub.b1-282 1597 L.sub.a2-16 L.sub.b1-282 1598 L.sub.a2-17 L.sub.b1-282 1599 L.sub.a2-18 L.sub.b1-282 1600 L.sub.a2-19 L.sub.b1-282 1601 L.sub.a2-20 L.sub.b1-282 1602 L.sub.a2-21 L.sub.b1-282 1603 L.sub.a2-22 L.sub.b1-282 1604 L.sub.a2-23 L.sub.b1-282 1605 L.sub.a2-31 L.sub.b1-282 1606 L.sub.a2-33 L.sub.b1-282 1607 L.sub.a2-46 L.sub.b1-282 1608 L.sub.a2-47 L.sub.b1-282 1609 L.sub.a2-48 L.sub.b1-282 1610 L.sub.a2-49 L.sub.b1-282 1611 L.sub.a2-50 L.sub.b1-282 1612 L.sub.a2-51 L.sub.b1-282 1613 L.sub.a2-52 L.sub.b1-282 1614 L.sub.a2-53 L.sub.b1-282 1615 L.sub.a2-54 L.sub.b1-282 1616 L.sub.a2-55 L.sub.b1-282 1617 L.sub.a2-56 L.sub.b1-282 1618 L.sub.a2-57 L.sub.b1-282 1619 L.sub.a2-58 L.sub.b1-282 1620 L.sub.a2-59 L.sub.b1-282 1621 L.sub.a2-60 L.sub.b1-282 1622 L.sub.a2-61 L.sub.b1-282 1623 L.sub.a2-62 L.sub.b1-282 1624 L.sub.a2-63 L.sub.b1-282 1625 L.sub.a2-64 L.sub.b1-282 1626 L.sub.a2-65 L.sub.b1-282 1627 L.sub.a2-66 L.sub.b1-282 1628 L.sub.a2-67 L.sub.b1-282 1629 L.sub.a2-149 L.sub.b1-282 1630 L.sub.a2-150 L.sub.b1-282 1631 L.sub.a2-151 L.sub.b1-282 1632 L.sub.a2-152 L.sub.b1-282 1633 L.sub.a2-153 L.sub.b1-282 1634 L.sub.a2-154 L.sub.b1-282 1635 L.sub.a2-155 L.sub.b1-282 1636 L.sub.a2-156 L.sub.b1-282 1637 L.sub.a2-157 L.sub.b1-282 1638 L.sub.a2-158 L.sub.b1-282 1639 L.sub.a2-159 L.sub.b1-282 1640 L.sub.a2-160 L.sub.b1-282 1641 L.sub.a3-1 L.sub.b1-282 1642 L.sub.3-6 L.sub.b1-282 1643 L.sub.a3-7 L.sub.b1-282 1644 L.sub.a3-20 L.sub.b1-282 1645 L.sub.a3-21 L.sub.b1-282 1646 L.sub.a3-23 L.sub.b1-282 1647 L.sub.a3-22 L.sub.b1-282 1648 L.sub.a3-25 L.sub.b1-282 1649 L.sub.a3-41 L.sub.b1-282 1650 L.sub.a3-42 L.sub.b1-282 1651 L.sub.a3-43 L.sub.b1-282 1652 L.sub.a3-44 L.sub.b1-282 1653 L.sub.a3-54 L.sub.b1-282 1654 L.sub.a3-55 L.sub.b1-282 1655 L.sub.a3-73 L.sub.b1-282 1656 L.sub.a3-74 L.sub.b1-282 1657 L.sub.a3-75 L.sub.b1-282 1658 L.sub.a3-76 L.sub.b1-282 1659 L.sub.a3-77 L.sub.b1-282 1660 L.sub.a3-78 L.sub.b1-282 1661 L.sub.a3-79 L.sub.b1-282 1662 L.sub.a3-80 L.sub.b1-282 1663 L.sub.a3-81 L.sub.b1-282 1664 L.sub.a3-82 L.sub.b1-282 1665 L.sub.a3-83 L.sub.b1-282 1666 L.sub.a3-84 L.sub.b1-282 1667 L.sub.a3-85 L.sub.b1-282 1668 L.sub.a3-86 L.sub.b1-282 1669 L.sub.a3-87 L.sub.b1-282 1670 L.sub.a3-88 L.sub.b1-282 1671 L.sub.a3-99 L.sub.b1-282 1672 L.sub.a3-100 L.sub.b1-282 1673 L.sub.a3-101 L.sub.b1-282 1674 L.sub.a3-102 L.sub.b1-282 1675 L.sub.a3-103 L.sub.b1-282 1676 L.sub.a3-104 L.sub.b1-282 1677 L.sub.a3-105 L.sub.b1-282 1678 L.sub.a3-106 L.sub.b1-282 1679 L.sub.a3-107 L.sub.b1-282 1680 L.sub.a3-108 L.sub.b1-282 1681 L.sub.a3-109 L.sub.b1-282 1682 L.sub.a3-110 L.sub.b1-282 1683 L.sub.a3-111 L.sub.b1-282 1684 L.sub.a3-127 L.sub.b1-282 1685 L.sub.a1-2 L.sub.b2-192 1686 L.sub.b2-192 L.sub.b2-192 1687 L.sub.a1-4 L.sub.b2-192 1688 L.sub.b2-192 L.sub.b2-192 1689 L.sub.a1-6 L.sub.b2-192 1690 L.sub.b2-192 L.sub.b2-192 1691 L.sub.a1-9 L.sub.b2-192 1692 L.sub.b2-192 L.sub.b2-192 1693 L.sub.a1-11 L.sub.b2-192 1694 L.sub.b2-192 L.sub.b2-192 1695 L.sub.a1-13 L.sub.b2-192 1696 L.sub.b2-192 L.sub.b2-192 1697 L.sub.a1-15 L.sub.b2-192 1698 L.sub.b2-192 L.sub.b2-192 1699 L.sub.a1-17 L.sub.b2-192 1700 L.sub.b2-192 L.sub.b2-192 1701 L.sub.a1-19 L.sub.b2-192 1702 L.sub.b2-192 L.sub.b2-192 1703 L.sub.a1-21 L.sub.b2-192 1704 L.sub.b2-192 L.sub.b2-192 1705 L.sub.a1-23 L.sub.b2-192 1706 L.sub.b2-192 L.sub.b2-192 1707 L.sub.a1-25 L.sub.b2-192 1708 L.sub.b2-192 L.sub.b2-192 1709 L.sub.a1-27 L.sub.b2-192 1710 L.sub.b2-192 L.sub.b2-192 1711 L.sub.a1-29 L.sub.b2-192 1712 L.sub.b2-192 L.sub.b2-192 1713 L.sub.a1-31 L.sub.b2-192 1714 L.sub.b2-192 L.sub.b2-192 1715 L.sub.a1-33 L.sub.b2-192 1716 L.sub.b2-192 L.sub.b2-192 1717 L.sub.a1-35 L.sub.b2-192 1718 L.sub.b2-192 L.sub.b2-192 1719 L.sub.a1-37 L.sub.b2-192 1720 L.sub.b2-192 L.sub.b2-192 1721 L.sub.a1-39 L.sub.b2-192 1722 L.sub.b2-192 L.sub.b2-192 1723 L.sub.a1-41 L.sub.b2-192 1724 L.sub.b2-192 L.sub.b2-192 1725 L.sub.a1-43 L.sub.b2-192 1726 L.sub.b2-192 L.sub.b2-192 1727 L.sub.a1-45 L.sub.b2-192 1728 L.sub.b2-192 L.sub.b2-192 1729 L.sub.a1-47 L.sub.b2-192 1730 L.sub.b2-192 L.sub.b2-192 1731 L.sub.a1-49 L.sub.b2-192 1732 L.sub.b2-192 L.sub.b2-192 1733 L.sub.a1-51 L.sub.b2-192 1734 L.sub.b2-192 L.sub.b2-192 1735 L.sub.a1-90 L.sub.b2-192 1736 L.sub.b2-192 L.sub.b2-192 1737 L.sub.a1-92 L.sub.b2-192 1738 L.sub.b2-192 L.sub.b2-192 1739 L.sub.a1-94 L.sub.b2-192 1740 L.sub.b2-192 L.sub.b2-192 1741 L.sub.a1-96 L.sub.b2-192 1742 L.sub.b2-192 L.sub.b2-192 1743 L.sub.a1-98 L.sub.b2-192 1744 L.sub.b2-192 L.sub.b2-192 1745 L.sub.a1-100 L.sub.b2-192 1746 L.sub.b2-192 L.sub.b2-192 1747 L.sub.a1-102 L.sub.b2-192 1748 L.sub.b2-192 L.sub.b2-192 1749 L.sub.a1-104 L.sub.b2-192 1750 L.sub.b2-192 L.sub.b2-192 1751 L.sub.a1-106 L.sub.b2-192 1752 L.sub.b2-192 L.sub.b2-192 1753 L.sub.a1-108 L.sub.b2-192 1754 L.sub.b2-192 L.sub.b2-192 1755 L.sub.a1-110 L.sub.b2-192 1756 L.sub.b2-192 L.sub.b2-192 1757 L.sub.a1-112 L.sub.b2-192 1758 L.sub.b2-192 L.sub.b2-192 1759 L.sub.a1-114 L.sub.b2-192 1760 L.sub.b2-192 L.sub.b2-192 1761 L.sub.a1-116 L.sub.b2-192 1762 L.sub.b2-192 L.sub.b2-192 1763 L.sub.a1-139 L.sub.b2-192 1764 L.sub.b2-192 L.sub.b2-192 1765 L.sub.a1-141 L.sub.b2-192 1766 L.sub.b2-192 L.sub.b2-192 1767 L.sub.a1-143 L.sub.b2-192 1768 L.sub.b2-192 L.sub.b2-192 1769 L.sub.a1-145 L.sub.b2-192 1770 L.sub.b2-192 L.sub.b2-192 1771 L.sub.a1-147 L.sub.b2-192 1772 L.sub.b2-192 L.sub.b2-192 1773 L.sub.a1-149 L.sub.b2-192 1774 L.sub.b2-192 L.sub.b2-192 1775 L.sub.a1-151 L.sub.b2-192 1776 L.sub.b2-192 L.sub.b2-192 1777 L.sub.a1-153 L.sub.b2-192 1778 L.sub.b2-192 L.sub.b2-192 1779 L.sub.a1-155 L.sub.b2-192 1780 L.sub.b2-192 L.sub.b2-192 1781 L.sub.a1-157 L.sub.b2-192 1782 L.sub.b2-192 L.sub.b2-192 1783 L.sub.a1-159 L.sub.b2-192 1784 L.sub.b2-192 L.sub.b2-192 1785 L.sub.a1-161 L.sub.b2-192 1786 L.sub.b2-192 L.sub.b2-192 1787 L.sub.a1-163 L.sub.b2-192 1788 L.sub.b2-192 L.sub.b2-192 1789 L.sub.a1-165 L.sub.b2-192 1790 L.sub.b2-192 L.sub.b2-192 1791 L.sub.a1-167 L.sub.b2-192 1792 L.sub.b2-192 L.sub.b2-192 1793 L.sub.a1-169 L.sub.b2-192 1794 L.sub.b2-192 L.sub.b2-192 1795 L.sub.a1-171 L.sub.b2-192 1796 L.sub.b2-192 L.sub.b2-192 1797 L.sub.a1-173 L.sub.b2-192 1798 L.sub.b2-192 L.sub.b2-192 1799 L.sub.a1-175 L.sub.b2-192 1800 L.sub.b2-192 L.sub.b2-192 1801 L.sub.a1-177 L.sub.b2-192 1802 L.sub.b2-192 L.sub.b2-192 1803 L.sub.a1-179 L.sub.b2-192 1804 L.sub.b2-192 L.sub.b2-192 1805 L.sub.a1-181 L.sub.b2-192 1806 L.sub.b2-192 L.sub.b2-192 1807 L.sub.a1-183 L.sub.b2-192 1808 L.sub.b2-192 L.sub.b2-192 1809 L.sub.a1-185 L.sub.b2-192 1810 L.sub.b2-192 L.sub.b2-192 1811 L.sub.a2-2 L.sub.b2-192 1812 L.sub.b2-192 L.sub.b2-192 1813 L.sub.a2-4 L.sub.b2-192 1814 L.sub.b2-192 L.sub.b2-192 1815 L.sub.a2-6 L.sub.b2-192 1816 L.sub.b2-192 L.sub.b2-192 1817 L.sub.a2-8 L.sub.b2-192 1818 L.sub.b2-192 L.sub.b2-192 1819 L.sub.a2-16 L.sub.b2-192 1820 L.sub.b2-192 L.sub.b2-192 1821 L.sub.a2-18 L.sub.b2-192 1822 L.sub.b2-192 L.sub.b2-192 1823 L.sub.a2-20 L.sub.b2-192 1824 L.sub.b2-192 L.sub.b2-192 1825 L.sub.a2-22 L.sub.b2-192 1826 L.sub.b2-192 L.sub.b2-192 1827 L.sub.a2-31 L.sub.b2-192 1828 L.sub.b2-192 L.sub.b2-192 1829 L.sub.a2-46 L.sub.b2-192 1830 L.sub.b2-192 L.sub.b2-192 1831 L.sub.a2-48 L.sub.b2-192 1832 L.sub.b2-192 L.sub.b2-192 1833 L.sub.a2-50 L.sub.b2-192 1834 L.sub.b2-192 L.sub.b2-192 1835 L.sub.a2-52 L.sub.b2-192 1836 L.sub.b2-192 L.sub.b2-192 1837 L.sub.a2-54 L.sub.b2-192 1838 L.sub.b2-192 L.sub.b2-192 1839 L.sub.a2-56 L.sub.b2-192 1840 L.sub.b2-192 L.sub.b2-192 1841 L.sub.a2-58 L.sub.b2-192 1842 L.sub.b2-192 L.sub.b2-192 1843 L.sub.a2-60 L.sub.b2-192 1844 L.sub.b2-192 L.sub.b2-192 1845 L.sub.a2-62 L.sub.b2-192 1846 L.sub.b2-192 L.sub.b2-192 1847 L.sub.a2-64 L.sub.b2-192 1848 L.sub.b2-192 L.sub.b2-192 1849 L.sub.a2-66 L.sub.b2-192 1850 L.sub.b2-192 L.sub.b2-192 1851 L.sub.a2-149 L.sub.b2-192 1852 L.sub.b2-192 L.sub.b2-192 1853 L.sub.a2-151 L.sub.b2-192 1854 L.sub.b2-192 L.sub.b2-192 1855 L.sub.a2-153 L.sub.b2-192 1856 L.sub.b2-192 L.sub.b2-192 1857 L.sub.a2-155 L.sub.b2-192 1858 L.sub.b2-192 L.sub.b2-192 1859 L.sub.a2-157 L.sub.b2-192 1860 L.sub.b2-192 L.sub.b2-192 1861 L.sub.a2-159 L.sub.b2-192 1862 L.sub.b2-192 L.sub.b2-192 1863 L.sub.a3-1 L.sub.b2-192 1864 L.sub.b2-192 L.sub.b2-192 1865 L.sub.a3-7 L.sub.b2-192 1866 L.sub.b2-192 L.sub.b2-192 1867 L.sub.a3-21 L.sub.b2-192 1868 L.sub.b2-192 L.sub.b2-192 1869 L.sub.a3-22 L.sub.b2-192 1870 L.sub.b2-192 L.sub.b2-192 1871 L.sub.a3-41 L.sub.b2-192 1872 L.sub.b2-192 L.sub.b2-192 1873 L.sub.a3-43 L.sub.b2-192 1874 L.sub.b2-192 L.sub.b2-192 1875 L.sub.a3-54 L.sub.b2-192 1876 L.sub.b2-192 L.sub.b2-192 1877 L.sub.a3-73 L.sub.b2-192 1878 L.sub.b2-192 L.sub.b2-192 1879 L.sub.a3-75 L.sub.b2-192 1880 L.sub.b2-192 L.sub.b2-192 1881 L.sub.a3-77 L.sub.b2-192 1882 L.sub.b2-192 L.sub.b2-192 1883 L.sub.a3-79 L.sub.b2-192 1884 L.sub.b2-192 L.sub.b2-192 1885 L.sub.a3-81 L.sub.b2-192 1886 L.sub.b2-192 L.sub.b2-192 1887 L.sub.a3-83 L.sub.b2-192 1888 L.sub.b2-192 L.sub.b2-192 1889 L.sub.a3-85 L.sub.b2-192 1890 L.sub.b2-192 L.sub.b2-192 1891 L.sub.a3-87 L.sub.b2-192 1892 L.sub.b2-192 L.sub.b2-192 1893 L.sub.a3-99 L.sub.b2-192 1894 L.sub.b2-192 L.sub.b2-192 1895 L.sub.a3-101 L.sub.b2-192 1896 L.sub.b2-192 L.sub.b2-192 1897 L.sub.a3-103 L.sub.b2-192 1898 L.sub.b2-192 L.sub.b2-192 1899 L.sub.a3-105 L.sub.b2-192 1900 L.sub.b2-192 L.sub.b2-192 1901 L.sub.a3-107 L.sub.b2-192 1902 L.sub.b2-192 L.sub.b2-192 1903 L.sub.a3-109 L.sub.b2-192 1904 L.sub.b2-192 L.sub.b2-192 1905 L.sub.a3-111 L.sub.b2-192 1906 L.sub.b2-192 L.sub.b2-192 1907 L.sub.a1-2 L.sub.b3-66 1908 L.sub.a1-3 L.sub.b3-66 1909 L.sub.a1-4 L.sub.b3-66 1910 L.sub.a1-5 L.sub.b3-66 1911 L.sub.a1-6 L.sub.b3-66 1912 L.sub.a1-7 L.sub.b3-66 1913 L.sub.a1-9 L.sub.b3-66 1914 L.sub.a1-10 L.sub.b3-66 1915 L.sub.a1-11 L.sub.b3-66 1916 L.sub.a1-12 L.sub.b3-66 1917 L.sub.a1-13 L.sub.b3-66 1918 L.sub.a1-14 L.sub.b3-66 1919 L.sub.a1-15 L.sub.b3-66 1920 L.sub.a1-16 L.sub.b3-66 1921 L.sub.a1-17 L.sub.b3-66 1922 L.sub.a1-18 L.sub.b3-66 1923 L.sub.a1-19 L.sub.b3-66 1924 L.sub.a1-20 L.sub.b3-66 1925 L.sub.a1-21 L.sub.b3-66 1926 L.sub.a1-22 L.sub.b3-66 1927 L.sub.a1-23 L.sub.b3-66 1928 L.sub.a1-24 L.sub.b3-66 1929 L.sub.a1-25 L.sub.b3-66 1930 L.sub.a1-26 L.sub.b3-66 1931 L.sub.a1-27 L.sub.b3-66 1932 L.sub.a1-28 L.sub.b3-66 1933 L.sub.a1-29 L.sub.b3-66 1934 L.sub.a1-30 L.sub.b3-66 1935 L.sub.a1-31 L.sub.b3-66 1936 L.sub.a1-32 L.sub.b3-66 1937 L.sub.a1-33 L.sub.b3-66 1938 L.sub.a1-34 L.sub.b3-66 1939 L.sub.a1-35 L.sub.b3-66 1940 L.sub.a1-36 L.sub.b3-66 1941 L.sub.a1-37 L.sub.b3-66 1942 L.sub.a1-38 L.sub.b3-66 1943 L.sub.a1-39 L.sub.b3-66 1944 L.sub.a1-40 L.sub.b3-66 1945 L.sub.a1-41 L.sub.b3-66 1946 L.sub.a1-42 L.sub.b3-66 1947 L.sub.a1-43 L.sub.b3-66 1948 L.sub.a1-44 L.sub.b3-66 1949 L.sub.a1-45 L.sub.b3-66 1950 L.sub.a1-46 L.sub.b3-66 1951 L.sub.a1-47 L.sub.b3-66 1952 L.sub.a1-48 L.sub.b3-66 1953 L.sub.a1-49 L.sub.b3-66 1954 L.sub.a1-50 L.sub.b3-66 1955 L.sub.a1-51 L.sub.b3-66 1956 L.sub.a1-52 L.sub.b3-66 1957 L.sub.a1-90 L.sub.b3-66 1958 L.sub.a1-91 L.sub.b3-66 1959 L.sub.a1-92 L.sub.b3-66 1960 L.sub.a1-93 L.sub.b3-66 1961 L.sub.a1-94 L.sub.b3-66 1962 L.sub.a1-95 L.sub.b3-66 1963 L.sub.a1-96 L.sub.b3-66 1964 L.sub.a1-97 L.sub.b3-66 1965 L.sub.a1-98 L.sub.b3-66 1966 L.sub.a1-99 L.sub.b3-66 1967 L.sub.a1-100 L.sub.b3-66 1968 L.sub.a1-101 L.sub.b3-66 1969 L.sub.a1-102 L.sub.b3-66 1970 L.sub.a1-103 L.sub.b3-66 1971 L.sub.a1-104 L.sub.b3-66 1972 L.sub.a1-105 L.sub.b3-66 1973 L.sub.a1-106 L.sub.b3-66 1974 L.sub.a1-107 L.sub.b3-66 1975 L.sub.a1-108 L.sub.b3-66 1976 L.sub.a1-109 L.sub.b3-66 1977 L.sub.a1-110 L.sub.b3-66 1978 L.sub.a1-111 L.sub.b3-66 1979 L.sub.a1-112 L.sub.b3-66 1980 L.sub.a1-113 L.sub.b3-66 1981 L.sub.a1-114 L.sub.b3-66 1982 L.sub.a1-115 L.sub.b3-66 1983 L.sub.a1-116 L.sub.b3-66 1984 L.sub.a1-117 L.sub.b3-66 1985 L.sub.a1-139 L.sub.b3-66 1986 L.sub.a1-140 L.sub.b3-66 1987 L.sub.a1-141 L.sub.b3-66 1988 L.sub.a1-142 L.sub.b3-66 1989 L.sub.a1-143 L.sub.b3-66 1990 L.sub.a1-144 L.sub.b3-66 1991 L.sub.a1-145 L.sub.b3-66 1992 L.sub.a1-146 L.sub.b3-66 1993 L.sub.a1-147 L.sub.b3-66 1994 L.sub.a1-148 L.sub.b3-66 1995 L.sub.a1-149 L.sub.b3-66 1996 L.sub.a1-150 L.sub.b3-66 1997 L.sub.a1-151 L.sub.b3-66 1998 L.sub.a1-152 L.sub.b3-66 1999 L.sub.a1-153 L.sub.b3-66 2000 L.sub.a1-154 L.sub.b3-66 2001 L.sub.a1-155 L.sub.b3-66 2002 L.sub.a1-156 L.sub.b3-66 2003 L.sub.a1-157 L.sub.b3-66 2004 L.sub.a1-158 L.sub.b3-66 2005 L.sub.a1-159 L.sub.b3-66 2006 L.sub.a1-160 L.sub.b3-66 2007 L.sub.a1-161 L.sub.b3-66 2008 L.sub.a1-162 L.sub.b3-66 2009 L.sub.a1-163 L.sub.b3-66 2010 L.sub.a1-164 L.sub.b3-66 2011 L.sub.a1-165 L.sub.b3-66 2012 L.sub.a1-166 L.sub.b3-66 2013 L.sub.a1-167 L.sub.b3-66 2014 L.sub.a1-168 L.sub.b3-66 2015 L.sub.a1-169 L.sub.b3-66 2016 L.sub.a1-170 L.sub.b3-66 2017 L.sub.a1-171 L.sub.b3-66 2018 L.sub.a1-172 L.sub.b3-66 2019 L.sub.a1-173 L.sub.b3-66 2020 L.sub.a1-174 L.sub.b3-66 2021 L.sub.a1-175 L.sub.b3-66 2022 L.sub.a1-176 L.sub.b3-66 2023 L.sub.a1-177 L.sub.b3-66 2024 L.sub.a1-178 L.sub.b3-66 2025 L.sub.a1-179 L.sub.b3-66 2026 L.sub.a1-180 L.sub.b3-66 2027 L.sub.a1-181 L.sub.b3-66 2028 L.sub.a1-182 L.sub.b3-66 2029 L.sub.a1-183 L.sub.b3-66 2030 L.sub.a1-184 L.sub.b3-66 2031 L.sub.a1-185 L.sub.b3-66 2032 L.sub.a1-186 L.sub.b3-66 2033 L.sub.a2-2 L.sub.b3-66 2034 L.sub.a2-3 L.sub.b3-66 2035 L.sub.a2-4 L.sub.b3-66 2036 L.sub.a2-5 L.sub.b3-66 2037 L.sub.a2-6 L.sub.b3-66 2038 L.sub.a2-7 L.sub.b3-66 2039 L.sub.a2-8 L.sub.b3-66 2040 L.sub.a2-9 L.sub.b3-66 2041 L.sub.a2-16 L.sub.b3-66 2042 L.sub.a2-17 L.sub.b3-66 2043 L.sub.a2-18 L.sub.b3-66 2044 L.sub.a2-19 L.sub.b3-66 2045 L.sub.a2-20 L.sub.b3-66 2046 L.sub.a2-21 L.sub.b3-66 2047 L.sub.a2-22 L.sub.b3-66 2048 L.sub.a2-23 L.sub.b3-66 2049 L.sub.a2-31 L.sub.b3-66 2050 L.sub.a2-33 L.sub.b3-66 2051 L.sub.a2-46 L.sub.b3-66 2052 L.sub.a2-47 L.sub.b3-66 2053 L.sub.a2-48 L.sub.b3-66 2054 L.sub.a2-49 L.sub.b3-66 2055 L.sub.a2-50 L.sub.b3-66 2056 L.sub.a2-51 L.sub.b3-66 2057 L.sub.a2-52 L.sub.b3-66 2058 L.sub.a2-53 L.sub.b3-66 2059 L.sub.a2-54 L.sub.b3-66 2060 L.sub.a2-55 L.sub.b3-66 2061 L.sub.a2-56 L.sub.b3-66 2062 L.sub.a2-57 L.sub.b3-66 2063 L.sub.a2-58 L.sub.b3-66 2064 L.sub.a2-59 L.sub.b3-66 2065 L.sub.a2-60 L.sub.b3-66 2066 L.sub.a2-61 L.sub.b3-66 2067 L.sub.a2-62 L.sub.b3-66 2068 L.sub.a2-63 L.sub.b3-66 2069 L.sub.a2-64 L.sub.b3-66 2070 L.sub.a2-65 L.sub.b3-66 2071 L.sub.a2-66 L.sub.b3-66 2072 L.sub.a2-67 L.sub.b3-66 2073 L.sub.a2-149 L.sub.b3-66 2074 L.sub.a2-150 L.sub.b3-66 2075 L.sub.a2-151 L.sub.b3-66 2076 L.sub.a2-152 L.sub.b3-66 2077 L.sub.a2-153 L.sub.b3-66 2078 L.sub.a2-154 L.sub.b3-66 2079 L.sub.a2-155 L.sub.b3-66 2080 L.sub.a2-156 L.sub.b3-66 2081 L.sub.a2-157 L.sub.b3-66 2082 L.sub.a2-158 L.sub.b3-66 2083 L.sub.a2-159 L.sub.b3-66 2084 L.sub.a2-160 L.sub.b3-66 2085 L.sub.a3-1 L.sub.b3-66 2086 L.sub.3-6 L.sub.b3-66 2087 L.sub.a3-7 L.sub.b3-66 2088 L.sub.a3-20 L.sub.b3-66 2089 L.sub.a3-21 L.sub.b3-66 2090 L.sub.a3-23 L.sub.b3-66 2091 L.sub.a3-22 L.sub.b3-66 2092 L.sub.a3-25 L.sub.b3-66 2093 L.sub.a3-41 L.sub.b3-66 2094 L.sub.a3-42 L.sub.b3-66 2095 L.sub.a3-43 L.sub.b3-66 2096 L.sub.a3-44 L.sub.b3-66 2097 L.sub.a3-54 L.sub.b3-66 2098 L.sub.a3-55 L.sub.b3-66 2099 L.sub.a3-73 L.sub.b3-66 2100 L.sub.a3-74 L.sub.b3-66 2101 L.sub.a3-75 L.sub.b3-66 2102 L.sub.a3-76 L.sub.b3-66 2103 L.sub.a3-77 L.sub.b3-66 2104 L.sub.a3-78 L.sub.b3-66 2105 L.sub.a3-79 L.sub.b3-66 2106 L.sub.a3-80 L.sub.b3-66 2107 L.sub.a3-81 L.sub.b3-66 2108 L.sub.a3-82 L.sub.b3-66 2109 L.sub.a3-83 L.sub.b3-66 2110 L.sub.a3-84 L.sub.b3-66 2111 L.sub.a3-85 L.sub.b3-66 2112 L.sub.a3-86 L.sub.b3-66 2113 L.sub.a3-87 L.sub.b3-66 2114 L.sub.a3-88 L.sub.b3-66 2115 L.sub.a3-99 L.sub.b3-66 2116 L.sub.a3-100 L.sub.b3-66 2117 L.sub.a3-101 L.sub.b3-66 2118 L.sub.a3-102 L.sub.b3-66 2119 L.sub.a3-103 L.sub.bS-66 2120 L.sub.a3-104 L.sub.b3-66 2121 L.sub.a3-105 L.sub.b3-66 2122 L.sub.a3-106 L.sub.b3-66 2123 L.sub.a3-107 L.sub.b3-66 2124 L.sub.a3-108 L.sub.b3-66 2125 L.sub.a3-109 L.sub.b3-66 2126 L.sub.a3-110 L.sub.b3-66 2127 L.sub.a3-111 L.sub.b3-66 2128 L.sub.a3-127 L.sub.b3-66
21. An electroluminescent device, comprising: an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein at least one layer of the organic layer comprises the metal complex according to claim 1.
22. The electroluminescent device according to claim 21, wherein the organic layer comprising the metal complex is an emissive layer.
23. The electroluminescent device according to claim 22, wherein the emissive layer further comprises a first host compound; preferably, the emissive layer further comprises a second host compound; and more preferably, the first host compound and/or the second host compound comprises at least one chemical group selected from the group consisting of: benzene, pyridine, pyrimidine, triazine, carbazole, azacarbazole, indolocarbazole, dibenzothiophene, azadibenzothiophene, dibenzofuran, azadibenzofuran, dibenzoselenophene, triphenylene, azatriphenylene, fluorene, silafluorene, naphthalene, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene, azaphenanthrene and combinations thereof.
24. The electroluminescent device according to claim 23, wherein 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 emissive layer; and preferably, the weight of the metal complex accounts for 3% to 13% of the total weight of the emissive layer.
25. A compound composition, comprising the metal complex according to claim 1.
Description
BRIEF DESCRIPTION OF DRAWINGS
[0044]
[0045]
DETAILED DESCRIPTION
[0046] OLEDs can be fabricated on various types of substrates such as glass, plastic, and metal foil.
[0047] The figures are not necessarily drawn to scale. Some of the layers in the figures can also be omitted as needed. Device 100 may include a substrate 101, an anode 110, a hole injection layer 120, a hole transport layer 130, an electron blocking layer 140, an emissive layer 150, a hole blocking layer 160, an electron transport layer 170, an electron injection layer 180 and a cathode 190. Device 100 may be fabricated by depositing the layers described in order. The properties and functions of these various layers, as well as example materials, are described in more detail in U.S. Pat. No. 7,279,704 at cols. 6-10, the contents of which are incorporated by reference herein in its entirety.
[0048] 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.
[0049] 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.
[0050] 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.
[0051] An OLED can be encapsulated by a barrier layer.
[0052] 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.
[0053] The materials and structures described herein may be used in other organic electronic devices listed above.
[0054] 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.
[0055] 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.
[0056] 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.
[0057] 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).
[0058] 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.
[0059] 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 (ΔE.sub.S-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 ΔE.sub.S-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
[0060] Halogen or halide—as used herein includes fluorine, chlorine, bromine, and iodine.
[0061] 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, an 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.
[0062] 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.
[0063] 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, and trimethylsilylisopropyl, triisopropylsilylmethyl, triisopropylsilylethyl. Additionally, the heteroalkyl group may be optionally substituted.
[0064] 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.
[0065] 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.
[0066] Aryl or an aromatic group—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.
[0067] Heterocyclic groups or heterocycle—as used herein include non-aromatic cyclic groups. Non-aromatic heterocyclic groups include 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.
[0068] Heteroaryl—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.
[0069] 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.
[0070] 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.
[0071] 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.
[0072] 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.
[0073] 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.
[0074] 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.
[0075] Arylgermanyl—as used herein contemplates a 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.
[0076] 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.
[0077] 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 having 6 to 20 carbon atoms, unsubstituted alkylgermanyl having 3 to 20 carbon atoms, unsubstituted arylgermanyl group 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.
[0078] 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.
[0079] 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 can 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.
[0080] 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 be the same structure or different structures.
[0081] 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.
[0082] 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:
##STR00010##
[0083] 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:
##STR00011##
[0084] 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:
##STR00012##
[0085] 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:
##STR00013##
[0086] According to an embodiment of the present disclosure, disclosed is a metal complex having a general formula of M(L.sub.a).sub.m(L.sub.b).sub.n(L.sub.c).sub.q;
[0087] wherein
[0088] 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.a, L.sub.b and L.sub.c are the same or different; wherein L.sub.a, L.sub.b and L.sub.c can be optionally joined to form a multidentate ligand;
[0089] the metal M is selected from a metal with a relative atomic mass greater than 40; and
[0090] m is selected from 1 or 2, n is selected from 1 or 2, q is selected from 0 or 1, and m+n+q equals an oxidation state of M; when m is 2, two L.sub.a are identical or different; when n is 2, two L.sub.b are identical or different;
[0091] L.sub.a has, at each occurrence identically or differently, a structure represented by Formula 1A and L.sub.b has, at each occurrence identically or differently, a structure represented by Formula 1B:
##STR00014##
[0092] wherein
[0093] the ring Cy1 is, at each occurrence identically or differently, selected from a heteroaromatic ring having 5 to 6 ring atoms;
[0094] the ring Cy2 is, at each occurrence identically or differently, selected from a benzene ring or a heteroaromatic ring having 5 to 6 ring atoms;
[0095] Ar 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;
[0096] a, b, c, d and e are, at each occurrence identically or differently, selected from 0 or 1, and at least one of a, b, c and d is selected from 1;
[0097] Z is, at each occurrence identically or differently, selected from O or X═X;
[0098] X is, at each occurrence identically or differently, selected from N or CR′;
[0099] U.sub.1 to U.sub.6 are, at each occurrence identically or differently, selected from CR.sub.u or N;
[0100] R″ is, at each occurrence identically or differently, selected from mono-substitution, multiple substitutions or non-substitution;
[0101] R′, R″ 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;
[0102] “*” represents a position where the ring Cy1 or the ring Cy2 is joined;
[0103] in Formula 1A, adjacent substituents R.sub.u can be optionally joined to form a ring;
[0104] in Formula 1B, adjacent substituents R′ and R″ can be optionally joined to form a ring; and
[0105] R.sub.1 is, at each occurrence identically or differently, selected from the group consisting of: substituted or unsubstituted alkyl having 4 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 4 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 4 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 4 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 4 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 4 to 20 carbon atoms, substituted or unsubstituted alkynyl having 4 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 4 to 30 carbon atoms and combinations thereof;
[0106] R.sub.2 has a structure represented by Formula 2:
##STR00015##
[0107] wherein
[0108] the number of carbon atoms in R.sub.2 is greater than or equal to 4;
[0109] R.sub.3, R.sub.4 and R.sub.5 are, at each occurrence identically or differently, selected from the group consisting of: 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;
##STR00016##
represents a position where Formula 2 is joined to Formula 1A;
[0110] two adjacent substituents of R.sub.3, R.sub.4 and R.sub.5 can be optionally joined to form a ring; and
[0111] L.sub.c is a mono anionic bidentate ligand.
[0112] In the present disclosure, the expression “adjacent substituents R′ and R″ 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 adjacent substituents R′, and 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.
[0113] In the present disclosure, the expression that “adjacent substituents R.sub.u can be optionally joined to form a ring” is intended to mean that when more than one of U.sub.1 to U.sub.6 are selected from CR.sub.u, any one or more of groups consisting of any two adjacent substituents R.sub.u can be joined to form a ring. Obviously, it is possible that none of these substituents are joined to forma ring.
[0114] In the present disclosure, the expression that “two adjacent substituents of R.sub.3, R.sub.4 and R.sub.5 can be optionally joined to form a ring” is intended to mean that any one or more of groups of adjacent substituents, such as substituents R.sub.3 and R.sub.4, substituents R.sub.4 and R.sub.5, and substituents R.sub.3 and R.sub.5, can be joined to form a ring. Obviously, it is possible that none of these substituents are joined to form a ring.
[0115] In the present disclosure, “a, b, c, d and e are, at each occurrence identically or differently, selected from 0 or 1” is intended to mean that when a to e are selected from 0, relevant substituents or groups are absent; when a to e are selected from 1, relevant substituents or groups are present. For example, when a is 0, it means that the ring Cy1 does not have the substituent Ar; when a is 1, it means that the ring Cy1 must have the substituent Ar. Similarly, other cases are explained in the same manner.
[0116] In the present disclosure, “Z is, at each occurrence identically or differently, selected from O or X═X” is intended to mean that
##STR00017##
has the following two structures:
##STR00018##
The two “*” in the ring Cy2 means that when c is 1, at least two adjacent C are present in the ring Cy2, and the ring Cy2 and
##STR00019##
can form any one of the following structures:
##STR00020##
when c is 0, the ring Cy2 is not joined to
##STR00021##
[0117] In the present disclosure, “e is, at each occurrence identically or differently, selected from 0 or 1” is intended to mean that when e is 0 or 1,
##STR00022##
has the structure
##STR00023##
respectively. The two “*” in the ring Cy1 means that when d is 1, at least two adjacent C are present in the ring Cy1, and the ring Cy1 is separately joined to
##STR00024##
to form the following structures:
##STR00025##
when d is 0, the ring Cy1 is not joined to
##STR00026##
[0118] According to an embodiment of the present disclosure, L.sub.c is, at each occurrence identically or differently, selected from a structure represented by any one of the group consisting of the following:
##STR00027##
[0119] wherein
[0120] R.sub.a, R.sub.b and R.sub.c represent, at each occurrence identically or differently, mono-substitution, multiple substitutions or non-substitution;
[0121] 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;
[0122] 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.N1, R.sub.C1 and R.sub.C2 can be optionally joined to form a ring.
[0123] In the present disclosure, the expression that “adjacent substituents R.sub.a, R.sub.b, 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, two 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.
[0124] According to an embodiment of the present disclosure, the ring Cy1 is, at each occurrence identically or differently, selected from any structure of the group consisting of the following:
##STR00028##
[0125] wherein “#” represents a position where the ring Cy1 is joined to the metal M, and
##STR00029##
represents a position where the ring Cy1 is joined to the ring Cy2.
[0126] According to an embodiment of the present disclosure, the ring Cy2 is, at each occurrence identically or differently, selected from any structure of the group consisting of the following:
##STR00030##
[0127] wherein “#” represents a position where the ring Cy2 is joined to the metal M, and
##STR00031##
represents a position where the ring Cy2 is joined to the ring Cy1.
[0128] According to an embodiment of the present disclosure, L.sub.b has a structure represented by any one of Formulas 1Ba to 1Bm:
##STR00032## ##STR00033## ##STR00034##
[0129] wherein
[0130] X.sub.1 to X.sub.8 are, at each occurrence identically or differently, selected from CR.sub.x or N;
[0131] Y.sub.1 to Y.sub.12 are, at each occurrence identically or differently, selected from CR.sub.y or N;
[0132] Ar 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;
[0133] R.sub.x and R.sub.y 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
[0134] adjacent substituents R.sub.x and R.sub.y can be optionally joined to form a ring.
[0135] In the present disclosure, the expression that “adjacent substituents R.sub.x and R.sub.y 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.x, two substituents R.sub.y, and substituents R.sub.x and R.sub.y, can be joined to form a ring. Obviously, it is possible that none of these substituents are joined to form a ring.
[0136] According to an embodiment of the present disclosure, L.sub.b has, at each occurrence identically or differently, a structure represented by any one of Formulas 1Ba to 1Bi.
[0137] According to an embodiment of the present disclosure, Ar is, at each occurrence identically or differently, selected from substituted or unsubstituted aryl having 6 to 24 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 24 carbon atoms or a combination thereof.
[0138] According to an embodiment of the present disclosure, Ar is, at each occurrence identically or differently, selected from substituted or unsubstituted aryl having 6 to 18 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 18 carbon atoms or a combination thereof.
[0139] According to an embodiment of the present disclosure, Ar is, at each occurrence identically or differently, selected from substituted or unsubstituted aryl having 6 to 12 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 12 carbon atoms or a combination thereof.
[0140] According to an embodiment of the present disclosure, Ar is, at each occurrence identically or differently, selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted pyridyl or a combination thereof.
[0141] According to an embodiment of the present disclosure, R.sub.1 is, at each occurrence identically or differently, selected from the group consisting of: substituted or unsubstituted alkyl having 4 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 4 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 4 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 4 to 20 ring atoms and combinations thereof.
[0142] According to an embodiment of the present disclosure, R.sub.1 is, at each occurrence identically or differently, selected from the group consisting of: substituted or unsubstituted alkyl having 4 to 10 carbon atoms, substituted or unsubstituted cycloalkyl having 4 to 10 ring carbon atoms and combinations thereof.
[0143] According to an embodiment of the present disclosure, R.sub.1 has a structure represented by Formula 2.
[0144] According to an embodiment of the present disclosure, wherein 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.
[0145] According to an embodiment of the present disclosure, wherein the metal M is, at each occurrence identically or differently, selected from Pt or Ir.
[0146] According to an embodiment of the present disclosure, R.sub.3, R.sub.4 and R.sub.5 are, at each occurrence identically or differently, selected from the group consisting of: 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 alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms or substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms.
[0147] According to an embodiment of the present disclosure, R.sub.3, R.sub.4 and R.sub.5 are, at each occurrence identically or differently, selected from the group consisting of: 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 and combinations thereof.
[0148] According to an embodiment of the present disclosure, R.sub.3, R.sub.4 and R.sub.5 are, at each occurrence identically or differently, selected from the group consisting of: halogen, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms and combinations thereof.
[0149] According to an embodiment of the present disclosure, the structure represented by Formula 2 represents, at each occurrence identically or differently, any one of the following structures:
##STR00035## ##STR00036##
[0150] wherein “*” represents a position where the structure is joined to Formula 1A; and
[0151] optionally, hydrogen atoms in the above structures can be partially or fully substituted with deuterium atoms.
[0152] According to an embodiment of the present disclosure, the metal complex has a structure of a general formula of Ir(L.sub.a).sub.m(L.sub.b).sub.3-m which is represented by Formula 3, Formula 4 or Formula 5:
##STR00037##
[0153] wherein
[0154] m is selected from 1 or 2; when m=1, two L.sub.b are identical or different; when m=2, two L.sub.a are identical or different;
[0155] X.sub.3 to X.sub.8 are, at each occurrence identically or differently, selected from CR.sub.x or N;
[0156] Y.sub.1 to Y.sub.8 are, at each occurrence identically or differently, selected from C, CR.sub.y or N;
[0157] U.sub.1 to U.sub.6 are, at each occurrence identically or differently, selected from CR.sub.u or N;
[0158] Ar 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;
[0159] R.sub.x, R.sub.y 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 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 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;
[0160] R.sub.3, R.sub.4 and R.sub.5 are, at each occurrence identically or differently, selected from the group consisting of: 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 alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms or substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms;
[0161] adjacent substituents R.sub.x and R.sub.y can be optionally joined to form a ring; and
[0162] two adjacent substituents of R.sub.3, R.sub.4 and R.sub.5 can be optionally joined to form a ring.
[0163] According to an embodiment of the present disclosure, the metal complex has a structure of the general formula of Ir(L.sub.a).sub.m(L.sub.b).sub.3-m which is represented by Formula 6, Formula 7, Formula 8 or Formula 9:
##STR00038## ##STR00039##
[0164] wherein
[0165] m is selected from 1 or 2; when m=1, two L.sub.b are identical or different; when m=2, two L.sub.a are identical or different;
[0166] R.sub.x, R.sub.y and R.sub.u represent, at each occurrence identically or differently, mono-substitution, multiple substitutions or non-substitution;
[0167] Ar 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;
[0168] R.sub.x, R.sub.y 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 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 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;
[0169] R.sub.3, R.sub.4 and R.sub.5 are, at each occurrence identically or differently, selected from the group consisting of: 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 alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms or substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms;
[0170] adjacent substituents R.sub.x and R.sub.y can be optionally joined to form a ring; and
[0171] two adjacent substituents of R.sub.3, R.sub.4 and R.sub.5 can be optionally joined to form a ring.
[0172] According to an embodiment of the present disclosure, 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 arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, a cyano group, a hydroxyl group, a sulfanyl group and combinations thereof.
[0173] According to an embodiment of the present disclosure, 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 heteroalkyl 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, a cyano group and combinations thereof.
[0174] According to an embodiment of the present disclosure, at least one of X.sub.3 to X.sub.8 is selected from CR.sub.x, and R.sub.x is selected from cyano or fluorine.
[0175] According to an embodiment of the present disclosure, at least one of X.sub.5 to X.sub.8 is selected from CR.sub.x, and R.sub.x is selected from cyano or fluorine.
[0176] According to an embodiment of the present disclosure, X.sub.7 or X.sub.8 is selected from CR.sub.x, and R.sub.x is selected from cyano or fluorine.
[0177] According to an embodiment of the present disclosure, at least two of X.sub.3 to X.sub.8 are selected from CR.sub.x, wherein one R.sub.x is selected from cyano or fluorine, and at least another one R.sub.x 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 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 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.
[0178] According to an embodiment of the present disclosure, at least two of X.sub.5 to X.sub.8 are selected from CR.sub.x, wherein one R.sub.x is selected from cyano or fluorine, and at least another one R.sub.x 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, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, a cyano group, a hydroxyl group, a sulfanyl group and combinations thereof.
[0179] According to an embodiment of the present disclosure, X.sub.7 and X.sub.8 are selected from CR.sub.x, wherein one R.sub.x is cyano, and another one R.sub.x 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.
[0180] According to an embodiment of the present disclosure, U.sub.1 to U.sub.6 are, at each occurrence identically or differently, selected from CR.sub.u.
[0181] According to an embodiment of the present disclosure, X.sub.1 to X.sub.8 are, at each occurrence identically or differently, selected from CR.sub.x.
[0182] According to an embodiment of the present disclosure, X.sub.3 to X.sub.8 are, at each occurrence identically or differently, selected from CR.sub.x.
[0183] According to an embodiment of the present disclosure, 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, R.sub.u 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 and combinations thereof.
[0185] According to an embodiment of the present disclosure, R.sub.u is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, substituted or unsubstituted alkyl having 1 to 10 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 10 ring carbon atoms, substituted or unsubstituted aryl having 6 to 10 carbon atoms and combinations thereof.
[0186] According to an embodiment of the present disclosure, R.sub.u is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, substituted or unsubstituted alkyl having 1 to 10 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 10 ring carbon atoms and combinations thereof.
[0187] According to an embodiment of the present disclosure, 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 aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms and combinations thereof.
[0188] According to an embodiment of the present disclosure, R.sub.y is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, substituted or unsubstituted alkyl having 1 to 10 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 10 ring carbon atoms, substituted or unsubstituted aryl having 6 to 10 carbon atoms and combinations thereof.
[0189] According to an embodiment of the present disclosure, R.sub.y is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, substituted or unsubstituted alkyl having 1 to 10 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 10 ring carbon atoms and combinations thereof.
[0190] According to an embodiment of the present disclosure, R′ and R″ 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 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 and combinations thereof.
[0191] According to an embodiment of the present disclosure, R′ and R″ are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, substituted or unsubstituted alkyl having 1 to 10 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 10 ring carbon atoms, substituted or unsubstituted alkenyl having 2 to 10 carbon atoms, substituted or unsubstituted aryl having 6 to 10 carbon atoms and combinations thereof.
[0192] According to an embodiment of the present disclosure, R′ and R″ are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, substituted or unsubstituted alkyl having 1 to 10 carbon atoms, substituted or unsubstituted alkenyl having 2 to 10 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 10 ring carbon atoms and combinations thereof.
[0193] According to an embodiment of the present disclosure, at least one of U.sub.1 to U.sub.3 is selected from N, for example, one of U.sub.1 to U.sub.3 is selected from N, or two of U.sub.1 to U.sub.3 are selected from N.
[0194] According to an embodiment of the present disclosure, at least one of U.sub.4 to U.sub.6 is selected from N, for example, one of U.sub.4 to U.sub.6 is selected from N, or two of U.sub.4 to U.sub.6 are selected from N.
[0195] According to an embodiment of the present disclosure, at least one of Y.sub.1 to Y.sub.4 is selected from N, for example, one of Y.sub.1 to Y.sub.4 is selected from N, or two of Y.sub.1 to Y.sub.4 are selected from N.
[0196] According to an embodiment of the present disclosure, at least one of X.sub.3 to X.sub.8 is selected from N, for example, one of X.sub.3 to X.sub.8 is selected from N, or two of X.sub.3 to X.sub.8 are selected from N.
[0197] 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.a1-231, L.sub.a2-1 to L.sub.a2-161 and L.sub.a3-1 to L.sub.a3-130, wherein the specific structures of L.sub.a1-1 to L.sub.a1-231, L.sub.a2-1 to L.sub.a2-161 and L.sub.a1-1 to L.sub.a3-130 are referred to claim 17.
[0198] According to an embodiment of the present disclosure, hydrogen atoms in L.sub.a1-1 to L.sub.a1-231, L.sub.a2-1 to L.sub.a2-161 and L.sub.a3-1 to L.sub.a3-130 can be partially or fully substituted with deuterium atoms.
[0199] 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.b1-1 to L.sub.b1-355, L.sub.b2-1 to L.sub.b2-261 and L.sub.b34 to L.sub.b3-650, wherein the specific structures of L.sub.b1-1 to L.sub.b1-355, L.sub.b2-1 to L.sub.b2-261 and L.sub.b3-1 to L.sub.b3-650 are referred to claim 18.
[0200] According to an embodiment of the present disclosure, hydrogen atoms in L.sub.b1-1 to L.sub.b1-355, L.sub.b2-1 to L.sub.b2-261 and L.sub.b34 to L.sub.b3-650 can be partially or fully substituted with deuterium atoms.
[0201] 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.c360 are referred to claim 19.
[0202] According to an embodiment of the present disclosure, the metal complex has a structure of Ir(L.sub.a).sub.2L.sub.b, wherein the two L.sub.a are identical or different, L.sub.a is, at each occurrence identically or differently, selected from the group consisting of L.sub.a1-1 to L.sub.a1-231, L.sub.a2-1 to L.sub.a2-161 and L.sub.a3-1 to L.sub.a3-130, and L.sub.b is selected from the group consisting of L.sub.b1-1 to L.sub.b1-355, L.sub.b2-1 to L.sub.b2-261 and L.sub.b3-1 to L.sub.b3-650.
[0203] According to an embodiment of the present disclosure, the metal complex has a structure of IrL.sub.a(L.sub.b).sub.2, wherein the two L.sub.b are identical or different, L.sub.a is selected from the group consisting of L.sub.a1-1 to L.sub.a1-231, L.sub.a2-1 to L.sub.a2-161 and L.sub.a3-1 to L.sub.a3-130, and L.sub.b is, at each occurrence identically or differently, selected from the group consisting of L.sub.b1-1 to L.sub.b1-355, L.sub.b2-1 to L.sub.b2-261 and L.sub.b3-1 to L.sub.b3-650.
[0204] 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 selected from the group consisting of L.sub.a1-1 to L.sub.a1-231, L.sub.a2-1 to L.sub.a1-161 and L.sub.a3-1 to L.sub.a3-130, L.sub.b is selected from the group consisting of L.sub.b1-1 to L.sub.b1-355, L.sub.b2-1 to L.sub.b2-261 and L.sub.b3-1 to L.sub.b3-650, and L.sub.c is selected from the group consisting of L.sub.c1 to L.sub.c360.
[0205] According to an embodiment of the present disclosure, the metal complex is selected from the group consisting of Metal Complex 1 to Metal Complex 2128, wherein the specific structures of Metal Complex 1 to Metal Complex 2128 are referred to claim 20.
[0206] According to an embodiment of the present disclosure, further disclosed is an electroluminescent device. The electroluminescent device includes:
[0207] an anode,
[0208] a cathode, and
[0209] an organic layer disposed between the anode and the cathode, wherein at least one layer of the organic layer comprises the metal complex according to any one of the preceding embodiments.
[0210] According to an embodiment of the present disclosure, the organic layer comprising the metal complex in the electroluminescent device is an emissive layer.
[0211] According to an embodiment of the present disclosure, the electroluminescent device emits green light.
[0212] According to an embodiment of the present disclosure, the emissive layer of the electroluminescent device further comprises a first host compound.
[0213] According to an embodiment of the present disclosure, the emissive layer of the electroluminescent device further comprises a first host compound and a second host compound.
[0214] According to an embodiment of the present disclosure, the first host compound and/or the second host compound in the electroluminescent device comprises at least one chemical group selected from the group consisting of: benzene, pyridine, pyrimidine, triazine, carbazole, azacarbazole, indolocarbazole, dibenzothiophene, azadibenzothiophene, dibenzofuran, azadibenzofuran, dibenzoselenophene, triphenylene, azatriphenylene, fluorene, silafluorene, naphthalene, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene, azaphenanthrene, and combinations thereof.
[0215] According to an embodiment of the present disclosure, the first host compound in the electroluminescent device has a structure represented by Formula X:
##STR00040##
[0216] wherein,
[0217] 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 combinations thereof;
[0218] 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 is attached to L.sub.x;
[0219] T is, at each occurrence identically or differently, selected from C, CR.sub.t or N, and at least one of T is C and is attached to L.sub.x;
[0220] R.sub.v and R.sub.t 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;
[0221] Ar.sub.1 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 combinations thereof;
[0222] adjacent substituents R.sub.v and R.sub.t can be optionally joined to form a ring.
[0223] Herein, the expression that “adjacent substituents R.sub.v and R.sub.t 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.t, and substituents R.sub.v and R.sub.t, can be joined to form a ring. Obviously, it is possible that none of these substituents are joined to form a ring. Obviously, it is possible that none of these substituents are joined to form a ring.
[0224] According to an embodiment of the present disclosure, the first host compound in the electroluminescent device has a structure represented by one of Formula X-a to Formula X-j:
##STR00041## ##STR00042##
[0225] wherein,
[0226] 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 combinations thereof;
[0227] V is, at each occurrence identically or differently, selected from CR.sub.v or N;
[0228] T is, at each occurrence identically or differently, selected from CR.sub.t or N;
[0229] R.sub.v and R.sub.t 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;
[0230] Ar.sub.1 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 combinations thereof;
[0231] adjacent substituents R.sub.v and R.sub.t can be optionally joined to form a ring.
[0232] 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 emissive layer.
[0233] 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 emissive layer.
[0234] According to another embodiment of the present disclosure, a compound composition is further disclosed. The compound composition comprises the metal complex described in any one of the above-mentioned embodiments.
[0235] Combination with Other Materials
[0236] 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.
[0237] 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.
[0238] 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.
Synthesis Example 1: Synthesis of Metal Complex 43
[0239] ##STR00043##
[0240] Intermediate 1 (2.9 g, 3.1 mmol), Intermediate 2 (1.5 g, 4.3 mmol), 2-ethoxyethanol (30 mL) and DMF (30 mL) were sequentially added into a dry 250 mL round-bottom flask and heated to react for 144 h at 90° C. under N.sub.2 protection. The solution was cooled, filtered through Celite, and washed twice with dichloromethane. The organic phases were collected, concentrated under reduced pressure, and purified through column chromatography to obtain Metal Complex 43 as a yellow solid (2.0 g, 1.9 mmol with a yield of 60%). The product was confirmed as the target product with a molecular weight of 1070.4.
Synthesis Example 2: Synthesis of Metal Complex 91
[0241] ##STR00044##
[0242] Intermediate 3 (1.1 g, 2.5 mmol), Intermediate 1 (1.7 g, 1.8 mmol), 2-ethoxyethanol (30 mL) and DMF (30 mL) were sequentially added into a dry 250 mL round-bottom flask and heated to react for 120 h at 100° C. under N.sub.2 protection. The solution was cooled, filtered through Celite, and washed twice with dichloromethane. The organic phases were collected, concentrated under reduced pressure, and purified through column chromatography to obtain Metal Complex 91 as a yellow solid (0.95 g, 0.8 mmol with a yield of 46%). The product was confirmed as the target product with a molecular weight of 1146.5.
Synthesis Example 3: Synthesis of Metal Complex 227
[0243] ##STR00045##
[0244] Intermediate 5 (0.75 g, 1.8 mmol), Intermediate 1 (0.9 g, 0.95 mmol), 2-ethoxyethanol (30 mL) and DMF (30 mL) were sequentially added into a dry 250 mL round-bottom flask and heated to react for 120 h at 100° C. under N.sub.2 protection. The solution was cooled, filtered through Celite, and washed twice with dichloromethane. The organic phases were collected, concentrated under reduced pressure, and purified through column chromatography to obtain Metal Complex 227 as a yellow solid (0.34 g, 0.2 mmol with a yield of 31%). The product was confirmed as the target product with a molecular weight of 1139.5.
Synthesis Example 4: Synthesis of Metal Complex 275
[0245] ##STR00046##
[0246] Intermediate 6 (0.45 g, 0.14 mmol), Intermediate 1 (0.88 g, 0.94 mmol) and ethanol (60 mL) were sequentially added into a dry 250 mL round-bottom flask and heated to reflux to react for 48 h under N.sub.2 protection. The reaction was cooled, filtered through Celite, and washed twice with methanol and n-hexane separately. Yellow solids on the Celite were dissolved with dichloromethane. The organic phases were collected, concentrated under reduced pressure, and purified through column chromatography to obtain Metal Complex 275 as a yellow solid (0.13 g, 0.1 mmol with a yield of 13.2%). The product was confirmed as the target product with a molecular weight of 1045.4.
Synthesis Example 5: Synthesis of Metal Complex 297
[0247] ##STR00047##
[0248] Intermediate 4 (1.0 g, 4.3 mmol), Intermediate 1 (3.1 g, 3.3 mmol), 2-ethoxyethanol (30 mL) and DMF (30 mL) were sequentially added into a dry 250 mL round-bottom flask and heated to reflux to react for 120 h under N.sub.2 protection. The reaction was cooled, filtered through Celite, and washed twice with methanol and n-hexane separately. Yellow solids on the Celite were dissolved with dichloromethane. The organic phases were collected, concentrated under reduced pressure, and purified through column chromatography to obtain Metal Complex 297 as a yellow solid (0.41 g, 0.43 mmol with a yield of 13%). The product was confirmed as the target product with a molecular weight of 955.4.
[0249] 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
[0250] 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 43 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 HB was deposited as a hole blocking layer (HBL). 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
[0251] The implementation mode in Device Comparative Example 1 was the same as that in Device Example 1, except that in the EML, Metal Complex 43 of the present disclosure was replaced with Compound GD1.
Device Comparative Example 2
[0252] The implementation mode in Device Comparative Example 2 was the same as that in Device Example 1, except that in the EML, Metal Complex 43 of the present disclosure was replaced with Compound GD2.
[0253] 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 Part of device structures in Example 1 and Comparative Examples 1 and 2 Device ID HIL HTL EBL EML HBL ETL Example 1 Compound HI Compound HT Compound H1 Compound Compound HB Compound (100 Å) (350 Å) (50 Å) H1:Compound (50 Å) ET:Liq H2:Metal Complex 43 (40:60) (46:46:8) (400 Å) (350 Å) Comparative Compound HI Compound HT Compound H1 Compound Compound HB Compound Example 1 (100 Å) (350 Å) (50 Å) H1:Compound (50 Å) ET:Liq H2:Compound GD1 (40:60) (46:46:8) (400 Å) (350 Å) Comparative Compound HI Compound HT Compound H1 Compound Compound HB Compound Example 2 (100 Å) (350 Å) (50 Å) H1:Compound (50 Å) ET:Liq H2:Compound GD2 (40:60) (46:46:8) (400 Å) (350 Å)
[0254] The structures of the materials used in the devices are shown as follows:
##STR00048## ##STR00049## ##STR00050##
[0255] Current-voltage-luminance (IVL) characteristics of the devices were measured. The CIE data, maximum emission wavelength λ.sub.max, current efficiency (CE) and external quantum efficiency (EQE) of each device were measured at 1000 cd/m.sup.2. The evaporation temperature (T.sub.Sub) of a material is the temperature tested when the metal complex is subjected to vacuum thermal evaporation at a rate of 0.2 angstroms per second and a vacuum degree of about 10.sup.−8 Torr. Lifetime (LT97) data was tested at a constant current of 80 mA/cm.sup.2. The data was recorded and shown in Table 2.
TABLE-US-00002 TABLE 2 Relevant data in Example 1 and Comparative Examples 1 and 2 T.sub.Sub CIE λ.sub.max CE EQE LT97 Device ID (° C.) (x, y) (nm) (cd/A) (%) (h) Example 1 241 (0.363, 0.619) 535 101 25.62 50.53 Comparative 250 (0.355, 0.625) 534 98 24.77 18.51 Example 1 Comparative 263 (0.346, 0.632) 531 100 25.38 36.01 Example 2
[0256] As can be seen from the data in Table 2, the metal complexes used in Example 1, Comparative Example 1 and Comparative Example 2 all have the same ligand L.sub.b; the metal complex in Example 1 differs from that in Comparative Example 1 merely in whether a substituent having four or more carbon atoms is present at a particular position of a six-membered heteroaromatic ring of the ligand L.sub.a; and the metal complex in Example 1 differs from that in Comparative Example 2 merely in whether a substituent having the structure of Formula 2 is present at a particular position of an aromatic ring of the ligand L.sub.a. Both the CE and EQE in Example 1 are superior to those in Comparative Example 1 and those in Comparative Example 2. In addition, it is particularly apparent that an increase in the lifetime in Example 1 is as high as 172% and 40.3% compared to that in Comparative Example 1 and that in Comparative Example 2, respectively, which is difficult for those skilled in the art to predict, indicating that a device with better performance may be obtained with the technical solution provided by the present disclosure. Moreover, Example 1 has an unexpectedly lower evaporation temperature than Comparative Example 1 and Comparative Example 2. The lower evaporation temperature indicates that the complex of the present disclosure has higher thermal stability in a process of preparing the device, which is conducive to industrial application of the material and can reduce energy consumption in industrialization.
Device Example 2
[0257] The implementation mode in Device Example 2 was the same as that in Device Example 1, except that in the EML, Metal Complex 43 of the present disclosure was replaced with Metal Complex 91.
Device Comparative Example 3
[0258] The implementation mode in Device Comparative Example 3 was the same as that in Device Example 1, except that in the EML, Metal Complex 43 of the present disclosure was replaced with Compound GD3.
Device Comparative Example 4
[0259] The implementation mode in Device Comparative Example 4 was the same as that in Device Example 1, except that in the EML, Metal Complex 43 of the present disclosure was replaced with Compound GD4.
Device Comparative Example 5
[0260] The implementation mode in Device Comparative Example 5 was the same as that in Device Example 1, except that in the EML, Metal Complex 43 of the present disclosure was replaced with Compound GD5.
[0261] 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 in Example 2 and Comparative Examples 3 to 5 Device ID HIL HTL EBL EML HBL ETL Example 2 Compound HI Compound HT Compound H1 Compound Compound HB Compound (100 Å) (350 Å) (50 Å) H1:Compound (50 Å) ET:Liq H2:Metal Complex 91 (40:60) (46:46:8) (400 Å) (350 Å) Comparative Compound HI Compound HT Compound H1 Compound Compound HB Compound Example 3 (100 Å) (350 Å) (50 Å) H1:Compound (50 Å) ET:Liq H2:Compound GD3 (40:60) (46:46:8) (400 Å) (350 Å) Comparative Compound HI Compound HT Compound H1 Compound Compound HB Compound Example 4 (100 Å) (350 Å) (50 Å) H1:Compound (50 Å) ET:Liq H2:Compound GD4 (40:60) (46:46:8) (400 Å) (350 Å) Comparative Compound HI Compound HT Compound H1 Compound Compound HB Compound Example 5 (100 Å) (350 Å) (50 Å) H1:Compound (50 Å) ET:Liq H2:Compound GD5 (40:60) (46:46:8) (400 Å) (350 Å)
[0262] The structures of the new materials used in the devices are shown as follows:
##STR00051##
[0263] IVL characteristics of the devices were measured. The CIE data, maximum emission wavelength λ.sub.max, FWHM, CE and EQE of each device were measured at 15 mA/cm.sup.2. The evaporation temperature (T.sub.Sub) of a material is the temperature tested when the metal complex is subjected to vacuum thermal evaporation at a rate of 0.2 angstroms per second and a vacuum degree of about 10.sup.−8 Torr. Lifetime (LT97) data was tested at a constant current of 80 mA/cm.sup.2. The data was recorded and shown in Table 4.
TABLE-US-00004 TABLE 4 Relevant data in Example 2 and Comparative Examples 3 to 5 T.sub.Sub CIE λ.sub.max FWHM CE EQE LT97 Device ID (° C.) (x, y) (nm) (nm) (cd/A) (%) (h) Example 2 273 (0.359, 0.623) 535 36.5 98 24.89 44.52 Comparative 290 (0.359, 0.623) 534 38.8 99 25.08 30.83 Example 3 Comparative 280 (0.355, 0.625) 534 42.0 97 24.78 25.01 Example 4 Comparative 308 (0.352, 0.627) 533 38.9 100 25.46 23.85 Example 5
[0264] As can be seen from the data in Table 4, the metal complexes used in Example 2 and Comparative Examples 3 to 5 all have the same ligand L.sub.b, and the metal complex in Example 2 differs from that in Comparative Examples 3 to 5 merely in substituent at a particular position of the ligand L.sub.a. In the case where the EQE in Example 2 and Comparative Examples 3 to 5 reaches a relatively high level, the lifetime in Example 2 is significantly improved by 44.4%, 78% and 86.7% compared to that in Comparative Examples 3 to 5, respectively, which is difficult for those skilled in the art to predict; Example 2 has a narrower FWHM, which is narrowed by 2.3 nm, 5.5 nm and 2.4 nm, respectively; moreover, Example 2 has a lower evaporation temperature, which is unexpectedly lowered by 17° C., 7° C. and 35° C., respectively. This further indicates that the device with better performance may be obtained with the technical solution provided by the present disclosure and that the complex of the present disclosure has higher thermal stability in the process of preparing the device, which is more conducive to the industrial application of the material and can reduce the energy consumption in the industrialization.
Device Example 3
[0265] The implementation mode in Device Example 3 was the same as that in Device Example 1, except that in the EML, Metal Complex 43 of the present disclosure was replaced with Metal Complex 275, and in the EML, the ratio of Compound H1, Compound H2 and Metal Complex 275 was 47:47:6.
Device Example 4
[0266] The implementation mode in Device Example 4 was the same as that in Device Example 1, except that in the EML, Metal Complex 43 of the present disclosure was replaced with Metal Complex 227.
Device Comparative Example 6
[0267] The implementation mode in Device Comparative Example 6 was the same as that in Device Example 3, except that in the EML, Metal Complex 275 of the present disclosure was replaced with Compound GD6.
Device Comparative Example 7
[0268] The implementation mode in Device Comparative Example 7 was the same as that in Device Example 1, except that in the EML, Metal Complex 43 of the present disclosure was replaced with Compound GD7.
Device Comparative Example 8
[0269] The implementation mode in Device Comparative Example 8 was the same as that in Device Example 1, except that in the EML, Metal Complex 43 of the present disclosure was replaced with Compound GD8.
[0270] 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-00005 TABLE 5 Device structures in Examples 3 and 4 and Comparative Examples 6 to 8 Device ID HIL HTL EBL EML HBL ETL Example 3 Compound HI Compound HT Compound H1 Compound Compound HB Compound (100 Å) (350 Å) (50 Å) H1:Compound (50 Å) ET:Liq H2:Metal Complex 275 (40:60) (47:47:6) (400 Å) (350 Å) Example 4 Compound HI Compound HT Compound H1 Compound Compound HB Compound (100 Å) (350 Å) (50 Å) H1:Compound (50 Å) ET:Liq H2:Metal Complex 227 (40:60) (46:46:8) (400 Å) (350 Å) Comparative Compound HI Compound HT Compound H1 Compound Compound HB Compound Example 6 (100 Å) (350 Å) (50 Å) H1:Compound (50 Å) ET:Liq H2:Compound GD6 (40:60) (47:47:6) (400 Å) (350 Å) Comparative Compound HI Compound HT Compound H1 Compound Compound HB Compound Example 7 (100 Å) (350 Å) (50 Å) H1:Compound (50 Å) ET:Liq H2:Compound GD7 (40:60) (46:46:8) (400 Å) (350 Å) Comparative Compound HI Compound HT Compound H1 Compound Compound HB Compound Example 8 (100 Å) (350 Å) (50 Å) H1:Compound (50 Å) ET:Liq H2:Compound GD8 (40:60) (46:46:8) (400 Å) (350 Å)
[0271] The structures of the new materials used in the devices are shown as follows:
##STR00052## ##STR00053##
[0272] IVL characteristics of the devices were measured. The CIE data, maximum emission wavelength λ.sub.max, FWHM, CE and EQE of each device were measured at 10 mA/cm.sup.2. The evaporation temperature (T.sub.Sub) of a material is the temperature tested when the metal complex is subjected to vacuum thermal evaporation at a rate of 0.2 angstroms per second and a vacuum degree of about 10.sup.−8 Torr. The data was recorded and shown in Table 6.
TABLE-US-00006 TABLE 6 Relevant data in Examples 3 and 4 and Comparative Examples 6 to 8 T.sub.Sub CIE λ.sub.max FWHM CE EQE Device ID (° C.) (x, y) (nm) (nm) (cd/A) (%) Example 3 249 (0.365, 0.614) 533 60.0 85 22.20 Comparative 258 (0.352, 0.623) 531 58.8 82 21.35 Example 6 Example 4 248 (0.374, 0.608) 534 60.5 94 24.58 Comparative 261 (0.375, 0.607) 534 61.6 90 23.51 Example 7 Comparative 292 (0.360, 0.618) 531 59.8 87 22.59 Example 8
[0273] As can be seen from the data in Table 6, the metal complexes of the present disclosure used in Example 3 and Comparative Example 6 both have the same ligand L.sub.b, and the metal complex in Example 3 differs from that in Comparative Example 6 merely in whether the substituent represented by Formula 2 is present at the particular position of the ligand L.sub.a. The CE and EQE in Example 3 are improved by 3.7% and 4.0% compared to those in Comparative Example 6, respectively. Moreover, the evaporation temperature in Example 3 is lowered by 9° C. compared to that in Comparative Example 6.
[0274] Similarly, Example 4 differs from Comparative Examples 7 and 8 merely in whether the substituent represented by Formula 2 is present at the particular position of the ligand L.sub.a. The CE and EQE in Example 4 are improved by 4.4% and 4.6% compared to those in Comparative Example 7, respectively. The CE and EQE in Example 4 are improved by 8.0% and 8.8% compared to those in Comparative Example 8, respectively. In the case where Comparative Examples 7 and 8 have excellent performance, the performance in Example 4 is very rare compared to that in Comparative Examples 7 and 8. Moreover, Example 4 has a lower evaporation temperature than Comparative Examples 7 and 8, and the evaporation temperature is lowered by 13° C. and 44° C., respectively.
[0275] The above results indicate that the device using the metal complex of the present disclosure can obtain better device performance and that the metal complex of the present disclosure has higher thermal stability in the process of preparing the device, which is more conducive to the industrial application of the material and can reduce the energy consumption in the industrialization.
[0276] To conclude, the metal complex comprising both the ligand L.sub.a having the structure of Formula 1A and the ligand L.sub.b having the structure of Formula 1B in the present application can obtain very excellent device performance, and in particular, an significant increase in device lifetime which is difficult to predict. Moreover, unexpectedly, the evaporation temperature can be lowered so that the metal complex of the present disclosure has higher thermal stability in the process of preparing the device, which is more conducive to the industrial application of the material and can reduce the energy consumption in the industrialization.
[0277] It is to 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 of 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 is to be understood that various theories as to why the present disclosure works are not intended to be limitative.