ORGANIC ELECTROLUMINESCENT MATERIAL AND DEVICE THEREOF
20230058719 · 2023-02-23
Assignee
Inventors
- Wei Cai (Beijing, CN)
- Hongbo Li (Beijing, CN)
- Zhen Wang (Beijing, CN)
- Ming Sang (Beijing, CN)
- Zheng Wang (Beijing, CN)
- Chi Yuen Raymond Kwong (Beijing, CN)
- Chuanjun Xia (Beijing, CN)
Cpc classification
H10K85/6574
ELECTRICITY
C09K2211/185
CHEMISTRY; METALLURGY
H10K85/6572
ELECTRICITY
C07B59/004
CHEMISTRY; METALLURGY
C07B2200/05
CHEMISTRY; METALLURGY
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 types of compound can be applied to an electroluminescent device to improve luminescence performance, efficiency or a lifetime of the device, exhibit more saturated luminescence and significantly improve overall performance of the device. Further provided are an 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 tetradentate ligand or 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 may be identical or different; when n is 2, two L.sub.b may be identical or different; wherein 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: ##STR00036## wherein Z is, at each occurrence identically or differently, selected from the group consisting of O, S, Se, NR′, CR′R′ and SiR′R′; when two R′ are present at the same time, the two R′ are identical or different; Cy is, at each occurrence identically or differently, selected from a substituted or unsubstituted aromatic ring having 6 to 24 ring atoms, a substituted or unsubstituted heteroaromatic ring having 5 to 24 ring atoms or a combination thereof, X.sub.1 to X.sub.8 are, at each occurrence identically or differently, selected from C, CR.sub.x or N, and at least one of X.sub.1 to X.sub.4 is selected from C and joined to Cy; at least one of X.sub.1 to X.sub.8 is selected from CR.sub.x, and the R.sub.x is cyano or fluorine; X.sub.1, X.sub.2, X.sub.3 or X.sub.4 is joined to the metal M by a metal-carbon bond or a metal-nitrogen bond; U.sub.1 to U.sub.4 are, at each occurrence identically or differently, selected from CR.sub.u or N; and W.sub.1 to W.sub.3 are, at each occurrence identically or differently, selected from CR.sub.w or N; wherein in Formula 1A, R.sub.A has a structure represented by Formula 2, and the total number of carbon atoms in Formula 2 is greater than or equal to 2: ##STR00037## wherein “*” represents a position where Formula 2 is joined to Formula 1A; R.sub.A1, R.sub.A2, R.sub.A3, R′, R.sub.x, R.sub.u and R.sub.w 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.A1, R.sub.A2, R.sub.A3, R′, R.sub.x, R.sub.u, R.sub.w 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 Cy is, at each occurrence identically or differently, selected from any structure of the group consisting of the following: ##STR00038## wherein R represents, at each occurrence identically or differently, mono-substitution, multiple substitutions or non-substitution; and when multiple R are present at the same time in any structure, the multiple R are the same or different; R is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof, adjacent substituents R can be optionally joined to form a ring; and “#” represents a position where Cy is joined to the metal M, and “ ##STR00039## ” represents a position where Cy is joined to X.sub.1, X.sub.2, X.sub.3 or X.sub.4.
3. The metal complex according to claim 1, wherein L.sub.b has a structure represented by any of Formulas 1Ba to 1Bf: ##STR00040## ##STR00041## wherein Z is, at each occurrence identically or differently, selected from the group consisting of O, S, Se, NR′, CR′R′ and SiR′R′; when two R′ are present at the same time, the two R′ are identical or different; X.sub.1 to X.sub.8 are, at each occurrence identically or differently, selected from CR.sub.x or N; at least one of X.sub.1 to X.sub.8 is selected from CR.sub.x, and the R.sub.x is cyano or fluorine; Y.sub.1 to Y.sub.4 are, at each occurrence identically or differently, selected from CR.sub.y or N; R′, 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 adjacent substituents R′, R.sub.x, R.sub.y can be optionally joined to form a ring.
4. The metal complex according to claim 1, wherein a metal complex Ir(L.sub.a).sub.m(L.sub.b).sub.3−m has a structure represented by Formula 3: ##STR00042## wherein Z is, at each occurrence identically or differently, selected from the group consisting of O, S, Se, NR′, CR′R′ and SiR′R′; when two R′ are present at the same time, the two R′ 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; at least one of X.sub.3 to X.sub.8 is selected from CR.sub.x, and the R.sub.x is cyano or fluorine; Y.sub.1 to Y.sub.4 are, at each occurrence identically or differently, selected from CR.sub.y or N; U.sub.1 to U.sub.4 are, at each occurrence identically or differently, selected from CR.sub.u or N; W.sub.1 to W.sub.3 are, at each occurrence identically or differently, selected from CR.sub.w or N; R.sub.A1, R.sub.A2, R.sub.A3, R′, R.sub.x, R.sub.y, R.sub.u and R.sub.v 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, the total number of carbon atoms in R.sub.A1, R.sub.A2 and R.sub.A3 is greater than or equal to 1; adjacent substituents R.sub.A1, R.sub.A2, R.sub.A3 can be optionally joined to form a ring; and adjacent substituents R′, R.sub.x, R.sub.y, R.sub.u, R.sub.w can be optionally joined to form a ring.
5. The metal complex according to claim 1, wherein Z is selected from the group consisting of: O and S; preferably, Z is O.
6. The metal complex according to claim 1, wherein X.sub.1 to X.sub.8 are, at each occurrence identically or differently, selected from C or CR.sub.x.
7. The metal complex according to claim 1, wherein at least one of X.sub.1 to X.sub.8 is selected from N; preferably, X.sub.8 is selected from N.
8. The metal complex according to claim 1, wherein W.sub.1 to W.sub.3 are, at each occurrence identically or differently, selected from CR.sub.w, and/or U.sub.1 to U.sub.4 are, at each occurrence identically or differently, selected from CR.sub.u; and R.sub.v and R.sub.u are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms and combinations thereof, preferably, R.sub.w and R.sub.u 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.w and R.sub.u 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.
9. The metal complex according to claim 3, wherein Y.sub.1 to Y.sub.4 are, at each occurrence identically or differently, selected from CR.sub.y, and 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, preferably, 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, and more preferably, 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.
10. The metal complex according to claim 1, wherein at least one of U.sub.1 to U.sub.4 is selected from CR.sub.u, and the R.sub.u is 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 and combinations thereof; preferably, at least one of U.sub.1 to U.sub.4 is selected from CR.sub.u, and the R.sub.u is selected from the group consisting of: substituted or unsubstituted alkyl having 3 to 12 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 12 ring carbon atoms and combinations thereof, and more preferably, U.sub.2 or U.sub.3 is selected from CR.sub.u, and the R.sub.u is selected from substituted or unsubstituted alkyl having 4 to 12 carbon atoms, substituted or unsubstituted cycloalkyl having 4 to 12 ring carbon atoms or a combination thereof.
11. The metal complex according to claim 1, wherein at least one of U.sub.1 to U.sub.4 is selected from CR.sub.u, and the R.sub.u has a structure represented by Formula 2; and preferably, U.sub.2 or U.sub.3 is selected from CR.sub.u, and the R.sub.u has a structure represented by Formula 2.
12. The metal complex according to claim 1, wherein the total number of carbon atoms in R.sub.A1, R.sub.A2 and R.sub.A3 is greater than or equal to 3; preferably, R.sub.A1, R.sub.A2 and R.sub.A3 are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 6 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 6 ring atoms, substituted or unsubstituted arylalkyl having 7 to 13 carbon atoms, substituted or unsubstituted aryl having 6 to 12 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 12 carbon atoms, a cyano group and combinations thereof, and the total number of carbon atoms in R.sub.A1, R.sub.A2 and R.sub.A3 is greater than or equal to 3; and more preferably, R.sub.A1, R.sub.A2 and R.sub.A3 are, at each occurrence identically or differently, selected from the group consisting of: substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms, substituted or unsubstituted aryl having 6 to 12 carbon atoms and combinations thereof.
13. The metal complex according to claim 1, wherein two of R.sub.A1, R.sub.A2 and R.sub.A3 are, identically or differently, selected from the group consisting of: substituted or unsubstituted alkyl having 1 to 6 carbon atoms or substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms; and another one of R.sub.A1, R.sub.A2 and R.sub.A3 is selected from the group consisting of: deuterium, fluorine, 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, a cyano group and combinations thereof, and preferably, two of R.sub.A1, R.sub.A2 and R.sub.A3 are, identically or differently, selected from the group consisting of: substituted or unsubstituted alkyl having 1 to 6 carbon atoms or substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms; and another one of R.sub.A1, R.sub.A2 and R.sub.A3 is selected from the group consisting of: deuterium, fluorine, substituted or unsubstituted aryl having 6 to 18 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 18 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 12 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 12 carbon atoms, a cyano group and combinations thereof.
14. The metal complex according to claim 1, wherein Formula 2 is, at each occurrence identically or differently, selected from the group consisting of the following: ##STR00043## ##STR00044## ##STR00045## ##STR00046## ##STR00047## ##STR00048## and combinations thereof; wherein “*” represents a position where Formula 2 is joined to Formula 1A; and optionally, hydrogen in the groups A-1 to A-83 can be partially or fully substituted with deuterium.
15. The metal complex according to claim 1, wherein at least one of X.sub.3 to X.sub.8 is selected from CR.sub.x, and the R.sub.x is cyano or fluorine; preferably, at least one of X.sub.5 to X.sub.8 is selected from CR.sub.x, and the R.sub.x is cyano or fluorine; and more preferably, at least one of X.sub.7 or X.sub.8 is selected from CR.sub.x, and the R.sub.x is cyano or fluorine.
16. The metal complex according to claim 1, wherein at least two of X.sub.3 to X.sub.8 are selected from CR.sub.x, one of the R.sub.x is selected from cyano or fluorine, and at least another one of the 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 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, preferably, at least two of X.sub.5 to X.sub.8 are selected from CR.sub.x, one of the R.sub.x is selected from cyano or fluorine, and at least another one of the 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, one of the R.sub.x is selected from cyano or fluorine, and another one of the R.sub.x is selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms, substituted or unsubstituted aryl having 6 to 12 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 12 carbon atoms and combinations 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: ##STR00049## ##STR00050## ##STR00051## ##STR00052## ##STR00053## ##STR00054## ##STR00055## ##STR00056## ##STR00057## ##STR00058## ##STR00059## ##STR00060## ##STR00061## ##STR00062## ##STR00063## ##STR00064## ##STR00065## ##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## wherein optionally, hydrogen in L.sub.a1−1 to L.sub.a1−123, L.sub.a2−1 to L.sub.a2−116 and L.sub.aD−1 to L.sub.aD−128 can be partially or fully substituted with deuterium.
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: ##STR00131## ##STR00132## ##STR00133## ##STR00134## ##STR00135## ##STR00136## ##STR00137## ##STR00138## ##STR00139## ##STR00140## ##STR00141## ##STR00142## ##STR00143## ##STR00144## ##STR00145## ##STR00146## ##STR00147## ##STR00148## ##STR00149## ##STR00150## ##STR00151## ##STR00152## ##STR00153## ##STR00154## ##STR00155## ##STR00156## ##STR00157## ##STR00158## ##STR00159## ##STR00160## ##STR00161## ##STR00162## ##STR00163## ##STR00164## ##STR00165## ##STR00166## ##STR00167## ##STR00168## ##STR00169## ##STR00170## ##STR00171## ##STR00172## ##STR00173## ##STR00174## ##STR00175## ##STR00176## ##STR00177## ##STR00178## ##STR00179## ##STR00180## ##STR00181## ##STR00182## ##STR00183## ##STR00184## ##STR00185## ##STR00186## ##STR00187## ##STR00188## ##STR00189## ##STR00190## ##STR00191## ##STR00192## ##STR00193## ##STR00194## ##STR00195## ##STR00196## ##STR00197## ##STR00198## ##STR00199## ##STR00200## ##STR00201## ##STR00202## ##STR00203## ##STR00204## ##STR00205## ##STR00206## ##STR00207## ##STR00208## ##STR00209## ##STR00210## ##STR00211## ##STR00212## ##STR00213## ##STR00214## ##STR00215## ##STR00216## ##STR00217## ##STR00218## ##STR00219## ##STR00220## ##STR00221## ##STR00222## ##STR00223## ##STR00224## ##STR00225## ##STR00226## ##STR00227## ##STR00228## ##STR00229## ##STR00230## ##STR00231## ##STR00232## ##STR00233## ##STR00234## ##STR00235## ##STR00236## ##STR00237## ##STR00238## ##STR00239## ##STR00240## ##STR00241## ##STR00242## ##STR00243## ##STR00244## ##STR00245## ##STR00246## ##STR00247## ##STR00248## ##STR00249## ##STR00250## ##STR00251## ##STR00252## ##STR00253## ##STR00254## ##STR00255## ##STR00256## ##STR00257## ##STR00258## wherein optionally, hydrogen in L.sub.b1−1 to L.sub.b1−357, L.sub.b2−1 to L.sub.b2−285 and L.sub.bx−1 to L.sub.bx−76 can be partially or fully substituted with deuterium.
19. The metal complex according to claim 1, wherein L.sub.c is, at each occurrence identically or differently, selected from the group consisting of the following: ##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##
20. The metal complex according to claim 1, wherein 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 selected from the group consisting of L.sub.a1−1 to L.sub.a1−23, L.sub.a2−1 to L.sub.a2−116 and L.sub.aD−1 to L.sub.aD−128, and L.sub.b is selected from the group consisting of L.sub.b1−1 to L.sub.b1−357, L.sub.b2−1 to L.sub.b2−285 and L.sub.bx−1 to L.sub.bx−76; preferably, the metal complex is selected from the group consisting of Metal Complex 1 to Metal Complex 1504, wherein Metal Complex 1 to Metal Complex 1504 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.b1-75 2 L.sub.a1-2 L.sub.b1-75 3 L.sub.a1-3 L.sub.b1-75 4 L.sub.a1-4 L.sub.b1-75 5 L.sub.a1-5 L.sub.b1-75 6 L.sub.a1-6 L.sub.b1-75 7 L.sub.a1-7 L.sub.b1-75 8 L.sub.a1-8 L.sub.b1-75 9 L.sub.a1-9 L.sub.b1-75 10 L.sub.a1-10 L.sub.b1-75 11 L.sub.a1-11 L.sub.b1-75 12 L.sub.a1-12 L.sub.b1-75 13 L.sub.a1-13 L.sub.b1-75 14 L.sub.a1-14 L.sub.b1-75 15 L.sub.a1-15 L.sub.b1-75 16 L.sub.a1-16 L.sub.b1-75 17 L.sub.a1-17 L.sub.b1-75 18 L.sub.a1-18 L.sub.b1-75 19 L.sub.a1-19 L.sub.b1-75 20 L.sub.a1-20 L.sub.b1-75 21 L.sub.a1-21 L.sub.b1-75 22 L.sub.a1-22 L.sub.b1-75 23 L.sub.a1-23 L.sub.b1-75 24 L.sub.a1-24 L.sub.b1-75 25 L.sub.a1-25 L.sub.b1-75 26 L.sub.a1-26 L.sub.b1-75 27 L.sub.a1-27 L.sub.b1-75 28 L.sub.a1-28 L.sub.b1-75 29 L.sub.a1-29 L.sub.b1-75 30 L.sub.a1-30 L.sub.b1-75 31 L.sub.a1-31 L.sub.b1-75 32 L.sub.a1-32 L.sub.b1-75 33 L.sub.a1-33 L.sub.b1-75 34 L.sub.a1-34 L.sub.b1-75 35 L.sub.a1-35 L.sub.b1-75 36 L.sub.a1-36 L.sub.b1-75 37 L.sub.a1-37 L.sub.b1-75 38 L.sub.a1-38 L.sub.b1-75 39 L.sub.a1-39 L.sub.b1-75 40 L.sub.a1-40 L.sub.b1-75 41 L.sub.a1-41 L.sub.b1-75 42 L.sub.a1-42 L.sub.b1-75 43 L.sub.a1-43 L.sub.b1-75 44 L.sub.a1-44 L.sub.b1-75 45 L.sub.a1-45 L.sub.b1-75 46 L.sub.a1-46 L.sub.b1-75 47 L.sub.a1-47 L.sub.b1-75 48 L.sub.a1-48 L.sub.b1-75 49 L.sub.a1-49 L.sub.b1-75 50 L.sub.a1-50 L.sub.b1-75 51 L.sub.a1-51 L.sub.b1-75 52 L.sub.a1-52 L.sub.b1-75 53 L.sub.a1-53 L.sub.b1-75 54 L.sub.a1-54 L.sub.b1-75 55 L.sub.a1-55 L.sub.b1-75 56 L.sub.a1-56 L.sub.b1-75 57 L.sub.a1-57 L.sub.b1-75 58 L.sub.a1-58 L.sub.b1-75 59 L.sub.a1-59 L.sub.b1-75 60 L.sub.a1-60 L.sub.b1-75 61 L.sub.a1-61 L.sub.b1-75 62 L.sub.a1-62 L.sub.b1-75 63 L.sub.a1-63 L.sub.b1-75 64 L.sub.a1-64 L.sub.b1-75 65 L.sub.a1-65 L.sub.b1-75 66 L.sub.a1-66 L.sub.b1-75 67 L.sub.a1-67 L.sub.b1-75 68 L.sub.a1-68 L.sub.b1-75 69 L.sub.a1-69 L.sub.b1-75 70 L.sub.a1-70 L.sub.b1-75 71 L.sub.a1-71 L.sub.b1-75 72 L.sub.a1-72 L.sub.b1-75 73 L.sub.a1-73 L.sub.b1-75 74 L.sub.a1-74 L.sub.b1-75 75 L.sub.a1-75 L.sub.b1-75 76 L.sub.a1-76 L.sub.b1-75 77 L.sub.a1-77 L.sub.b1-75 78 L.sub.a1-78 L.sub.b1-75 79 L.sub.a1-79 L.sub.b1-75 80 L.sub.a1-80 L.sub.b1-75 81 L.sub.a1-81 L.sub.b1-75 82 L.sub.a1-82 L.sub.b1-75 83 L.sub.a1-83 L.sub.b1-75 84 L.sub.a1-84 L.sub.b1-75 85 L.sub.a1-85 L.sub.b1-75 86 L.sub.a1-86 L.sub.b1-75 87 L.sub.a1-87 L.sub.b1-75 88 L.sub.a1-88 L.sub.b1-75 89 L.sub.a1-89 L.sub.b1-75 90 L.sub.a1-90 L.sub.b1-75 91 L.sub.a1-91 L.sub.b1-75 92 L.sub.a1-92 L.sub.b1-75 93 L.sub.a1-93 L.sub.b1-75 94 L.sub.a1-94 L.sub.b1-75 95 L.sub.a1-95 L.sub.b1-75 96 L.sub.a1-96 L.sub.b1-75 97 L.sub.a1-97 L.sub.b1-75 98 L.sub.a1-98 L.sub.b1-75 99 L.sub.a1-99 L.sub.b1-75 100 L.sub.a1-100 L.sub.b1-75 101 L.sub.a1-101 L.sub.b1-75 102 L.sub.a1-102 L.sub.b1-75 103 L.sub.a1-103 L.sub.b1-75 104 L.sub.a1-104 L.sub.b1-75 105 L.sub.a1-105 L.sub.b1-75 106 L.sub.a1-106 L.sub.b1-75 107 L.sub.a1-107 L.sub.b1-75 108 L.sub.a1-108 L.sub.b1-75 109 L.sub.a1-109 L.sub.b1-75 110 L.sub.a1-110 L.sub.b1-75 111 L.sub.a1-111 L.sub.b1-75 112 L.sub.a1-112 L.sub.b1-75 113 L.sub.a1-113 L.sub.b1-75 114 L.sub.a1-114 L.sub.b1-75 115 L.sub.a1-115 L.sub.b1-75 116 L.sub.a1-116 L.sub.b1-75 117 L.sub.a1-117 L.sub.b1-75 118 L.sub.a1-118 L.sub.b1-75 119 L.sub.a1-119 L.sub.b1-75 120 L.sub.a1-120 L.sub.b1-75 121 L.sub.a1-1 L.sub.b1-282 122 L.sub.a1-2 L.sub.b1-282 123 L.sub.a1-3 L.sub.b1-282 124 L.sub.a1-4 L.sub.b1-282 125 L.sub.a1-5 L.sub.b1-282 126 L.sub.a1-6 L.sub.b1-282 127 L.sub.a1-7 L.sub.b1-282 128 L.sub.a1-8 L.sub.b1-282 129 L.sub.a1-9 L.sub.b1-282 130 L.sub.a1-10 L.sub.b1-282 131 L.sub.a1-11 L.sub.b1-282 132 L.sub.a1-12 L.sub.b1-282 133 L.sub.a1-13 L.sub.b1-282 134 L.sub.a1-14 L.sub.b1-282 135 L.sub.a1-15 L.sub.b1-282 136 L.sub.a1-16 L.sub.b1-282 137 L.sub.a1-17 L.sub.b1-282 138 L.sub.a1-18 L.sub.b1-282 139 L.sub.a1-19 L.sub.b1-282 140 L.sub.a1-20 L.sub.b1-282 141 L.sub.a1-21 L.sub.b1-282 142 L.sub.a1-22 L.sub.b1-282 143 L.sub.a1-23 L.sub.b1-282 144 L.sub.a1-24 L.sub.b1-282 145 L.sub.a1-25 L.sub.b1-282 146 L.sub.a1-26 L.sub.b1-282 147 L.sub.a1-27 L.sub.b1-282 148 L.sub.a1-28 L.sub.b1-282 149 L.sub.a1-29 L.sub.b1-282 150 L.sub.a1-30 L.sub.b1-282 151 L.sub.a1-31 L.sub.b1-282 152 L.sub.a1-32 L.sub.b1-282 153 L.sub.a1-33 L.sub.b1-282 154 L.sub.a1-34 L.sub.b1-282 155 L.sub.a1-35 L.sub.b1-282 156 L.sub.a1-36 L.sub.b1-282 157 L.sub.a1-37 L.sub.b1-282 158 L.sub.a1-38 L.sub.b1-282 159 L.sub.a1-39 L.sub.b1-282 160 L.sub.a1-40 L.sub.b1-282 161 L.sub.a1-41 L.sub.b1-282 162 L.sub.a1-42 L.sub.b1-282 163 L.sub.a1-43 L.sub.b1-282 164 L.sub.a1-44 L.sub.b1-282 165 L.sub.a1-45 L.sub.b1-282 166 L.sub.a1-46 L.sub.b1-282 167 L.sub.a1-47 L.sub.b1-282 168 L.sub.a1-48 L.sub.b1-282 169 L.sub.a1-49 L.sub.b1-282 170 L.sub.a1-50 L.sub.b1-282 171 L.sub.a1-51 L.sub.b1-282 172 L.sub.a1-52 L.sub.b1-282 173 L.sub.a1-53 L.sub.b1-282 174 L.sub.a1-54 L.sub.b1-282 175 L.sub.a1-55 L.sub.b1-282 176 L.sub.a1-56 L.sub.b1-282 177 L.sub.a1-57 L.sub.b1-282 178 L.sub.a1-58 L.sub.b1-282 179 L.sub.a1-59 L.sub.b1-282 180 L.sub.a1-60 L.sub.b1-282 181 L.sub.a1-61 L.sub.b1-282 182 L.sub.a1-62 L.sub.b1-282 183 L.sub.a1-63 L.sub.b1-282 184 L.sub.a1-64 L.sub.b1-282 185 L.sub.a1-65 L.sub.b1-282 186 L.sub.a1-66 L.sub.b1-282 187 L.sub.a1-67 L.sub.b1-282 188 L.sub.a1-68 L.sub.b1-282 189 L.sub.a1-69 L.sub.b1-282 190 L.sub.a1-70 L.sub.b1-282 191 L.sub.a1-71 L.sub.b1-282 192 L.sub.a1-72 L.sub.b1-282 193 L.sub.a1-73 L.sub.b1-282 194 L.sub.a1-74 L.sub.b1-282 195 L.sub.a1-75 L.sub.b1-282 196 L.sub.a1-76 L.sub.b1-282 197 L.sub.a1-77 L.sub.b1-282 198 L.sub.a1-78 L.sub.b1-282 199 L.sub.a1-79 L.sub.b1-282 200 L.sub.a1-80 L.sub.b1-282 201 L.sub.a1-81 L.sub.b1-282 202 L.sub.a1-82 L.sub.b1-282 203 L.sub.a1-83 L.sub.b1-282 204 L.sub.a1-84 L.sub.b1-282 205 L.sub.a1-85 L.sub.b1-282 206 L.sub.a1-86 L.sub.b1-282 207 L.sub.a1-87 L.sub.b1-282 208 L.sub.a1-88 L.sub.b1-282 209 L.sub.a1-89 L.sub.b1-282 210 L.sub.a1-90 L.sub.b1-282 211 L.sub.a1-91 L.sub.b1-282 212 L.sub.a1-92 L.sub.b1-282 213 L.sub.a1-93 L.sub.b1-282 214 L.sub.a1-94 L.sub.b1-282 215 L.sub.a1-95 L.sub.b1-282 216 L.sub.a1-96 L.sub.b1-282 217 L.sub.a1-97 L.sub.b1-282 218 L.sub.a1-98 L.sub.b1-282 219 L.sub.a1-99 L.sub.b1-282 220 L.sub.a1-100 L.sub.b1-282 221 L.sub.a1-101 L.sub.b1-282 222 L.sub.a1-102 L.sub.b1-282 223 L.sub.a1-103 L.sub.b1-282 224 L.sub.a1-104 L.sub.b1-282 225 L.sub.a1-105 L.sub.b1-282 226 L.sub.a1-106 L.sub.b1-282 227 L.sub.a1-107 L.sub.b1-282 228 L.sub.a1-108 L.sub.b1-282 229 L.sub.a1-109 L.sub.b1-282 230 L.sub.a1-110 L.sub.b1-282 231 L.sub.a1-111 L.sub.b1-282 232 L.sub.a1-112 L.sub.b1-282 233 L.sub.a1-113 L.sub.b1-282 234 L.sub.a1-114 L.sub.b1-282 235 L.sub.a1-115 L.sub.b1-282 236 L.sub.a1-116 L.sub.b1-282 237 L.sub.a1-117 L.sub.b1-282 238 L.sub.a1-118 L.sub.b1-282 239 L.sub.a1-119 L.sub.b1-282 240 L.sub.a1-120 L.sub.b1-282 241 L.sub.a1-1 L.sub.b1-345 242 L.sub.a1-2 L.sub.b1-345 243 L.sub.a1-3 L.sub.b1-345 244 L.sub.a1-4 L.sub.b1-345 245 L.sub.a1-5 L.sub.b1-345 246 L.sub.a1-6 L.sub.b1-345 247 L.sub.a1-7 L.sub.b1-345 248 L.sub.a1-8 L.sub.b1-345 249 L.sub.a1-9 L.sub.b1-345 250 L.sub.a1-10 L.sub.b1-345 251 L.sub.a1-11 L.sub.b1-345 252 L.sub.a1-12 L.sub.b1-345 253 L.sub.a1-13 L.sub.b1-345 254 L.sub.a1-14 L.sub.b1-345 255 L.sub.a1-15 L.sub.b1-345 256 L.sub.a1-16 L.sub.b1-345 257 L.sub.a1-17 L.sub.b1-345 258 L.sub.a1-18 L.sub.b1-345 259 L.sub.a1-19 L.sub.b1-345 260 L.sub.a1-20 L.sub.b1-345 261 L.sub.a1-21 L.sub.b1-345 262 L.sub.a1-22 L.sub.b1-345 263 L.sub.a1-23 L.sub.b1-345 264 L.sub.a1-24 L.sub.b1-345 265 L.sub.a1-25 L.sub.b1-345 266 L.sub.a1-26 L.sub.b1-345 267 L.sub.a1-27 L.sub.b1-345 268 L.sub.a1-28 L.sub.b1-345 269 L.sub.a1-29 L.sub.b1-345 270 L.sub.a1-30 L.sub.b1-345 271 L.sub.a1-31 L.sub.b1-345 272 L.sub.a1-32 L.sub.b1-345 273 L.sub.a1-33 L.sub.b1-345 274 L.sub.a1-34 L.sub.b1-345 275 L.sub.a1-35 L.sub.b1-345 276 L.sub.a1-36 L.sub.b1-345 277 L.sub.a1-37 L.sub.b1-345 278 L.sub.a1-38 L.sub.b1-345 279 L.sub.a1-39 L.sub.b1-345 280 L.sub.a1-40 L.sub.b1-345 281 L.sub.a1-41 L.sub.b1-345 282 L.sub.a1-42 L.sub.b1-345 283 L.sub.a1-43 L.sub.b1-345 284 L.sub.a1-44 L.sub.b1-345 285 L.sub.a1-45 L.sub.b1-345 286 L.sub.a1-46 L.sub.b1-345 287 L.sub.a1-47 L.sub.b1-345 288 L.sub.a1-48 L.sub.b1-345 289 L.sub.a1-49 L.sub.b1-345 290 L.sub.a1-50 L.sub.b1-345 291 L.sub.a1-51 L.sub.b1-345 292 L.sub.a1-52 L.sub.b1-345 293 L.sub.a1-53 L.sub.b1-345 294 L.sub.a1-54 L.sub.b1-345 295 L.sub.a1-55 L.sub.b1-345 296 L.sub.a1-56 L.sub.b1-345 297 L.sub.a1-57 L.sub.b1-345 298 L.sub.a1-58 L.sub.b1-345 299 L.sub.a1-59 L.sub.b1-345 300 L.sub.a1-60 L.sub.b1-345 301 L.sub.a1-61 L.sub.b1-345 302 L.sub.a1-62 L.sub.b1-345 303 L.sub.a1-63 L.sub.b1-345 304 L.sub.a1-64 L.sub.b1-345 305 L.sub.a1-65 L.sub.b1-345 306 L.sub.a1-66 L.sub.b1-345 307 L.sub.a1-67 L.sub.b1-345 308 L.sub.a1-68 L.sub.b1-345 309 L.sub.a1-69 L.sub.b1-345 310 L.sub.a1-70 L.sub.b1-345 311 L.sub.a1-71 L.sub.b1-345 312 L.sub.a1-72 L.sub.b1-345 313 L.sub.a1-73 L.sub.b1-345 314 L.sub.a1-74 L.sub.b1-345 315 L.sub.a1-75 L.sub.b1-345 316 L.sub.a1-76 L.sub.b1-345 317 L.sub.a1-77 L.sub.b1-345 318 L.sub.a1-78 L.sub.b1-345 319 L.sub.a1-79 L.sub.b1-345 320 L.sub.a1-80 L.sub.b1-345 321 L.sub.a1-81 L.sub.b1-345 322 L.sub.a1-82 L.sub.b1-345 323 L.sub.a1-83 L.sub.b1-345 324 L.sub.a1-84 L.sub.b1-345 325 L.sub.a1-85 L.sub.b1-345 326 L.sub.a1-86 L.sub.b1-345 327 L.sub.a1-87 L.sub.b1-345 328 L.sub.a1-88 L.sub.b1-345 329 L.sub.a1-89 L.sub.b1-345 330 L.sub.a1-90 L.sub.b1-345 331 L.sub.a1-91 L.sub.b1-345 332 L.sub.a1-92 L.sub.b1-345 333 L.sub.a1-93 L.sub.b1-345 334 L.sub.a1-94 L.sub.b1-345 335 L.sub.a1-95 L.sub.b1-345 336 L.sub.a1-96 L.sub.b1-345 337 L.sub.a1-97 L.sub.b1-345 338 L.sub.a1-98 L.sub.b1-345 339 L.sub.a1-99 L.sub.b1-345 340 L.sub.a1-100 L.sub.b1-345 341 L.sub.a1-101 L.sub.b1-345 342 L.sub.a1-102 L.sub.b1-345 343 L.sub.a1-103 L.sub.b1-345 345 L.sub.a1-104 L.sub.b1-345 345 L.sub.a1-105 L.sub.b1-345 346 L.sub.a1-106 L.sub.b1-345 347 L.sub.a1-107 L.sub.b1-345 348 L.sub.a1-108 L.sub.b1-345 349 L.sub.a1-109 L.sub.b1-345 350 L.sub.a1-110 L.sub.b1-345 351 L.sub.a1-111 L.sub.b1-345 352 L.sub.a1-112 L.sub.b1-345 353 L.sub.a1-113 L.sub.b1-345 354 L.sub.a1-114 L.sub.b1-345 355 L.sub.a1-115 L.sub.b1-345 356 L.sub.a1-116 L.sub.b1-345 357 L.sub.a1-117 L.sub.b1-345 358 L.sub.a1-118 L.sub.b1-345 359 L.sub.a1-119 L.sub.b1-345 360 L.sub.a1-120 L.sub.b1-345 361 L.sub.a1-1 L.sub.b2-67 362 L.sub.a1-2 L.sub.b2-67 363 L.sub.a1-3 L.sub.b2-67 364 L.sub.a1-4 L.sub.b2-67 365 L.sub.a1-5 L.sub.b2-67 366 L.sub.a1-6 L.sub.b2-67 367 L.sub.a1-7 L.sub.b2-67 368 L.sub.a1-8 L.sub.b2-67 369 L.sub.a1-9 L.sub.b2-67 370 L.sub.a1-10 L.sub.b2-67 371 L.sub.a1-11 L.sub.b2-67 372 L.sub.a1-12 L.sub.b2-67 373 L.sub.a1-13 L.sub.b2-67 374 L.sub.a1-14 L.sub.b2-67 375 L.sub.a1-15 L.sub.b2-67 376 L.sub.a1-16 L.sub.b2-67 377 L.sub.a1-17 L.sub.b2-67 378 L.sub.a1-18 L.sub.b2-67 379 L.sub.a1-19 L.sub.b2-67 380 L.sub.a1-20 L.sub.b2-67 381 L.sub.a1-21 L.sub.b2-67 382 L.sub.a1-22 L.sub.b2-67 383 L.sub.a1-23 L.sub.b2-67 384 L.sub.a1-24 L.sub.b2-67 385 L.sub.a1-25 L.sub.b2-67 386 L.sub.a1-26 L.sub.b2-67 387 L.sub.a1-27 L.sub.b2-67 388 L.sub.a1-28 L.sub.b2-67 389 L.sub.a1-29 L.sub.b2-67 390 L.sub.a1-30 L.sub.b2-67 391 L.sub.a1-31 L.sub.b2-67 392 L.sub.a1-32 L.sub.b2-67 393 L.sub.a1-33 L.sub.b2-67 394 L.sub.a1-34 L.sub.b2-67 395 L.sub.a1-35 L.sub.b2-67 396 L.sub.a1-36 L.sub.b2-67 397 L.sub.a1-37 L.sub.b2-67 398 L.sub.a1-38 L.sub.b2-67 399 L.sub.a1-39 L.sub.b2-67 400 L.sub.a1-40 L.sub.b2-67 401 L.sub.a1-41 L.sub.b2-67 402 L.sub.a1-42 L.sub.b2-67 403 L.sub.a1-43 L.sub.b2-67 404 L.sub.a1-44 L.sub.b2-67 405 L.sub.a1-45 L.sub.b2-67 406 L.sub.a1-46 L.sub.b2-67 407 L.sub.a1-47 L.sub.b2-67 408 L.sub.a1-48 L.sub.b2-67 409 L.sub.a1-49 L.sub.b2-67 410 L.sub.a1-50 L.sub.b2-67 411 L.sub.a1-51 L.sub.b2-67 412 L.sub.a1-52 L.sub.b2-67 413 L.sub.a1-53 L.sub.b2-67 414 L.sub.a1-54 L.sub.b2-67 415 L.sub.a1-55 L.sub.b2-67 416 L.sub.a1-56 L.sub.b2-67 417 L.sub.a1-57 L.sub.b2-67 418 L.sub.a1-58 L.sub.b2-67 419 L.sub.a1-59 L.sub.b2-67 420 L.sub.a1-60 L.sub.b2-67 421 L.sub.a1-61 L.sub.b2-67 422 L.sub.a1-62 L.sub.b2-67 423 L.sub.a1-63 L.sub.b2-67 424 L.sub.a1-64 L.sub.b2-67 425 L.sub.a1-65 L.sub.b2-67 426 L.sub.a1-66 L.sub.b2-67 427 L.sub.a1-67 L.sub.b2-67 428 L.sub.a1-68 L.sub.b2-67 429 L.sub.a1-69 L.sub.b2-67 430 L.sub.a1-70 L.sub.b2-67 431 L.sub.a1-71 L.sub.b2-67 432 L.sub.a1-72 L.sub.b2-67 433 L.sub.a1-73 L.sub.b2-67 434 L.sub.a1-74 L.sub.b2-67 435 L.sub.a1-75 L.sub.b2-67 436 L.sub.a1-76 L.sub.b2-67 437 L.sub.a1-77 L.sub.b2-67 438 L.sub.a1-78 L.sub.b2-67 439 L.sub.a1-79 L.sub.b2-67 440 L.sub.a1-80 L.sub.b2-67 441 L.sub.a1-81 L.sub.b2-67 442 L.sub.a1-82 L.sub.b2-67 443 L.sub.a1-83 L.sub.b2-67 444 L.sub.a1-84 L.sub.b2-67 445 L.sub.a1-85 L.sub.b2-67 446 L.sub.a1-86 L.sub.b2-67 447 L.sub.a1-87 L.sub.b2-67 448 L.sub.a1-88 L.sub.b2-67 449 L.sub.a1-89 L.sub.b2-67 450 L.sub.a1-90 L.sub.b2-67 451 L.sub.a1-91 L.sub.b2-67 452 L.sub.a1-92 L.sub.b2-67 453 L.sub.a1-93 L.sub.b2-67 454 L.sub.a1-94 L.sub.b2-67 455 L.sub.a1-95 L.sub.b2-67 456 L.sub.a1-96 L.sub.b2-67 457 L.sub.a1-97 L.sub.b2-67 458 L.sub.a1-98 L.sub.b2-67 459 L.sub.a1-99 L.sub.b2-67 460 L.sub.a1-100 L.sub.b2-67 461 L.sub.a1-101 L.sub.b2-67 462 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531 L.sub.a1-51 L.sub.b2-192 532 L.sub.a1-52 L.sub.b2-192 533 L.sub.a1-53 L.sub.b2-192 534 L.sub.a1-54 L.sub.b2-192 535 L.sub.a1-55 L.sub.b2-192 536 L.sub.a1-56 L.sub.b2-192 537 L.sub.a1-57 L.sub.b2-192 538 L.sub.a1-58 L.sub.b2-192 539 L.sub.a1-59 L.sub.b2-192 540 L.sub.a1-60 L.sub.b2-192 541 L.sub.a1-61 L.sub.b2-192 542 L.sub.a1-62 L.sub.b2-192 543 L.sub.a1-63 L.sub.b2-192 544 L.sub.a1-64 L.sub.b2-192 545 L.sub.a1-65 L.sub.b2-192 546 L.sub.a1-66 L.sub.b2-192 547 L.sub.a1-67 L.sub.b2-192 548 L.sub.a1-68 L.sub.b2-192 549 L.sub.a1-69 L.sub.b2-192 550 L.sub.a1-70 L.sub.b2-192 551 L.sub.a1-71 L.sub.b2-192 552 L.sub.a1-72 L.sub.b2-192 553 L.sub.a1-73 L.sub.b2-192 554 L.sub.a1-74 L.sub.b2-192 555 L.sub.a1-75 L.sub.b2-192 556 L.sub.a1-76 L.sub.b2-192 557 L.sub.a1-77 L.sub.b2-192 558 L.sub.a1-78 L.sub.b2-192 559 L.sub.a1-79 L.sub.b2-192 560 L.sub.a1-80 L.sub.b2-192 561 L.sub.a1-81 L.sub.b2-192 562 L.sub.a1-82 L.sub.b2-192 563 L.sub.a1-83 L.sub.b2-192 564 L.sub.a1-84 L.sub.b2-192 565 L.sub.a1-85 L.sub.b2-192 566 L.sub.a1-86 L.sub.b2-192 567 L.sub.a1-87 L.sub.b2-192 568 L.sub.a1-88 L.sub.b2-192 569 L.sub.a1-89 L.sub.b2-192 570 L.sub.a1-90 L.sub.b2-192 571 L.sub.a1-91 L.sub.b2-192 572 L.sub.a1-92 L.sub.b2-192 573 L.sub.a1-93 L.sub.b2-192 574 L.sub.a1-94 L.sub.b2-192 575 L.sub.a1-95 L.sub.b2-192 576 L.sub.a1-96 L.sub.b2-192 577 L.sub.a1-97 L.sub.b2-192 578 L.sub.a1-98 L.sub.b2-192 579 L.sub.a1-99 L.sub.b2-192 580 L.sub.a1-100 L.sub.b2-192 581 L.sub.a1-101 L.sub.b2-192 582 L.sub.a1-102 L.sub.b2-192 583 L.sub.a1-103 L.sub.b2-192 584 L.sub.a1-104 L.sub.b2-192 585 L.sub.a1-105 L.sub.b2-192 586 L.sub.a1-106 L.sub.b2-192 587 L.sub.a1-107 L.sub.b2-192 588 L.sub.a1-108 L.sub.b2-192 589 L.sub.a1-109 L.sub.b2-192 590 L.sub.a1-110 L.sub.b2-192 591 L.sub.a1-111 L.sub.b2-192 592 L.sub.a1-112 L.sub.b2-192 593 L.sub.a1-113 L.sub.b2-192 594 L.sub.a1-114 L.sub.b2-192 595 L.sub.a1-115 L.sub.b2-192 596 L.sub.a1-116 L.sub.b2-192 597 L.sub.a1-117 L.sub.b2-192 598 L.sub.a1-118 L.sub.b2-192 599 L.sub.a1-119 L.sub.b2-192 600 L.sub.a1-120 L.sub.b2-192 601 L.sub.aD-1 L.sub.b1-1 602 L.sub.aD-1 L.sub.b1-2 603 L.sub.aD-1 L.sub.b1-3 604 L.sub.aD-1 L.sub.b1-4 605 L.sub.aD-1 L.sub.b1-5 606 L.sub.aD-1 L.sub.b1-6 607 L.sub.aD-1 L.sub.b1-7 608 L.sub.aD-1 L.sub.b1-8 609 L.sub.aD-1 L.sub.b1-9 610 L.sub.aD-1 L.sub.b1-10 611 L.sub.aD-1 L.sub.b1-11 612 L.sub.aD-1 L.sub.b1-12 613 L.sub.aD-1 L.sub.b1-13 614 L.sub.aD-1 L.sub.b1-14 615 L.sub.aD-1 L.sub.b1-15 616 L.sub.aD-1 L.sub.b1-16 617 L.sub.aD-1 L.sub.b1-17 618 L.sub.aD-1 L.sub.b1-18 619 L.sub.aD-1 L.sub.b1-45 620 L.sub.aD-1 L.sub.b1-49 621 L.sub.aD-1 L.sub.b1-50 622 L.sub.aD-1 L.sub.b1-57 623 L.sub.aD-1 L.sub.b1-58 624 L.sub.aD-1 L.sub.b1-59 625 L.sub.aD-1 L.sub.b1-60 626 L.sub.aD-1 L.sub.b1-61 627 L.sub.aD-1 L.sub.b1-71 628 L.sub.aD-1 L.sub.b1-72 629 L.sub.aD-1 L.sub.b1-73 630 L.sub.aD-1 L.sub.b1-74 631 L.sub.aD-1 L.sub.b1-75 632 L.sub.aD-1 L.sub.b1-76 633 L.sub.aD-1 L.sub.b1-77 634 L.sub.aD-1 L.sub.b1-78 635 L.sub.aD-1 L.sub.b1-79 636 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L.sub.b2-271 816 L.sub.aD-1 L.sub.b2-272 817 L.sub.aD-1 L.sub.b2-273 818 L.sub.aD-1 L.sub.b2-274 819 L.sub.aD-1 L.sub.b2-275 820 L.sub.aD-1 L.sub.bx-1 821 L.sub.aD-1 L.sub.bx-6 822 L.sub.aD-1 L.sub.bx-34 823 L.sub.aD-2 L.sub.b1-1 824 L.sub.aD-2 L.sub.b1-2 825 L.sub.aD-2 L.sub.b1-3 826 L.sub.aD-2 L.sub.b1-4 827 L.sub.aD-2 L.sub.b1-5 828 L.sub.aD-2 L.sub.b1-6 829 L.sub.aD-2 L.sub.b1-7 830 L.sub.aD-2 L.sub.b1-8 831 L.sub.aD-2 L.sub.b1-9 832 L.sub.aD-2 L.sub.b1-10 833 L.sub.aD-2 L.sub.b1-11 834 L.sub.aD-2 L.sub.b1-12 835 L.sub.aD-2 L.sub.b1-13 836 L.sub.aD-2 L.sub.b1-14 837 L.sub.aD-2 L.sub.b1-15 838 L.sub.aD-2 L.sub.b1-16 839 L.sub.aD-2 L.sub.b1-17 840 L.sub.aD-2 L.sub.b1-18 841 L.sub.aD-2 L.sub.b1-45 842 L.sub.aD-2 L.sub.b1-49 843 L.sub.aD-2 L.sub.b1-50 844 L.sub.aD-2 L.sub.b1-57 845 L.sub.aD-2 L.sub.b1-58 846 L.sub.aD-2 L.sub.b1-59 847 L.sub.aD-2 L.sub.b1-60 848 L.sub.aD-2 L.sub.b1-61 849 L.sub.aD-2 L.sub.b1-71 850 L.sub.aD-2 L.sub.b1-72 851 L.sub.aD-2 L.sub.b1-73 852 L.sub.aD-2 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L.sub.aD-12 L.sub.b1-57 1067 L.sub.aD-12 L.sub.b1-58 1068 L.sub.aD-12 L.sub.b1-59 1069 L.sub.aD-12 L.sub.b1-60 1070 L.sub.aD-12 L.sub.b1-61 1071 L.sub.aD-12 L.sub.b1-71 1072 L.sub.aD-12 L.sub.b1-72 1073 L.sub.aD-12 L.sub.b1-73 1074 L.sub.aD-12 L.sub.b1-74 1075 L.sub.aD-12 L.sub.b1-75 1076 L.sub.aD-12 L.sub.b1-76 1077 L.sub.aD-12 L.sub.b1-77 1078 L.sub.aD-12 L.sub.b1-78 1079 L.sub.aD-12 L.sub.b1-79 1080 L.sub.aD-12 L.sub.b1-80 1081 L.sub.aD-12 L.sub.b1-81 1082 L.sub.aD-12 L.sub.b1-82 1083 L.sub.aD-12 L.sub.b1-83 1084 L.sub.aD-12 L.sub.b1-84 1085 L.sub.aD-12 L.sub.b1-85 1086 L.sub.aD-12 L.sub.b1-86 1087 L.sub.aD-12 L.sub.b1-87 1088 L.sub.aD-12 L.sub.b1-88 1089 L.sub.aD-12 L.sub.b1-89 1090 L.sub.aD-12 L.sub.b1-90 1091 L.sub.aD-12 L.sub.b1-91 1092 L.sub.aD-12 L.sub.b1-92 1093 L.sub.aD-12 L.sub.b1-93 1094 L.sub.aD-12 L.sub.b1-94 1095 L.sub.aD-12 L.sub.b1-102 1096 L.sub.aD-12 L.sub.b1-103 1097 L.sub.aD-12 L.sub.b1-104 1098 L.sub.aD-12 L.sub.b1-105 1099 L.sub.aD-12 L.sub.b1-106 1100 L.sub.aD-12 L.sub.b1-107 1101 L.sub.aD-12 L.sub.b1-108 1102 L.sub.aD-12 L.sub.b1-109 1103 L.sub.aD-12 L.sub.b1-120 1104 L.sub.aD-12 L.sub.b1-121 1105 L.sub.aD-12 L.sub.b1-122 1106 L.sub.aD-12 L.sub.b1-123 1107 L.sub.aD-12 L.sub.b1-131 1108 L.sub.aD-12 L.sub.b1-132 1109 L.sub.aD-12 L.sub.b1-133 1110 L.sub.aD-12 L.sub.b1-134 1111 L.sub.aD-12 L.sub.b1-135 1112 L.sub.aD-12 L.sub.b1-136 1113 L.sub.aD-12 L.sub.b1-159 1114 L.sub.aD-12 L.sub.b1-160 1115 L.sub.aD-12 L.sub.b1-161 1116 L.sub.aD-12 L.sub.b1-162 1117 L.sub.aD-12 L.sub.b1-163 1118 L.sub.aD-12 L.sub.b1-164 1119 L.sub.aD-12 L.sub.b1-206 1120 L.sub.aD-12 L.sub.b1-207 1121 L.sub.aD-12 L.sub.b1-208 1122 L.sub.aD-12 L.sub.b1-209 1123 L.sub.aD-12 L.sub.b1-210 1124 L.sub.aD-12 L.sub.b1-211 1125 L.sub.aD-12 L.sub.b1-212 1126 L.sub.aD-12 L.sub.b1-213 1127 L.sub.aD-12 L.sub.b1-214 1128 L.sub.aD-12 L.sub.b1-215 1129 L.sub.aD-12 L.sub.b1-216 1130 L.sub.aD-12 L.sub.b1-217 1131 L.sub.aD-12 L.sub.b1-267 1132 L.sub.aD-12 L.sub.b1-268 1133 L.sub.aD-12 L.sub.b1-269 1134 L.sub.aD-12 L.sub.b1-270 1135 L.sub.aD-12 L.sub.b1-273 1136 L.sub.aD-12 L.sub.b1-275 1137 L.sub.aD-12 L.sub.b1-279 1138 L.sub.aD-12 L.sub.b1-280 1139 L.sub.aD-12 L.sub.b1-282 1140 L.sub.aD-12 L.sub.b1-283 1141 L.sub.aD-12 L.sub.b1-284 1142 L.sub.aD-12 L.sub.b1-285 1143 L.sub.aD-12 L.sub.b1-286 1144 L.sub.aD-12 L.sub.b1-287 1145 L.sub.aD-12 L.sub.b1-288 1146 L.sub.aD-12 L.sub.b1-289 1147 L.sub.aD-12 L.sub.b1-290 1148 L.sub.aD-12 L.sub.b1-291 1149 L.sub.aD-12 L.sub.b1-292 1150 L.sub.aD-12 L.sub.b1-293 1151 L.sub.aD-12 L.sub.b1-294 1152 L.sub.aD-12 L.sub.b1-295 1153 L.sub.aD-12 L.sub.b1-299 1154 L.sub.aD-12 L.sub.b1-300 1155 L.sub.aD-12 L.sub.b1-301 1156 L.sub.aD-12 L.sub.b1-302 1157 L.sub.aD-12 L.sub.b1-303 1158 L.sub.aD-12 L.sub.b1-304 1159 L.sub.aD-12 L.sub.b1-305 1160 L.sub.aD-12 L.sub.b1-306 1161 L.sub.aD-12 L.sub.b1-307 1162 L.sub.aD-12 L.sub.b1-308 1163 L.sub.aD-12 L.sub.b1-315 1164 L.sub.aD-12 L.sub.b1-316 1165 L.sub.aD-12 L.sub.b1-317 1166 L.sub.aD-12 L.sub.b1-318 1167 L.sub.aD-12 L.sub.b1-319 1168 L.sub.aD-12 L.sub.b1-320 1169 L.sub.aD-12 L.sub.b1-321 1170 L.sub.aD-12 L.sub.b1-322 1171 L.sub.aD-12 L.sub.b1-323 1172 L.sub.aD-12 L.sub.b1-324 1173 L.sub.aD-12 L.sub.b1-325 1174 L.sub.aD-12 L.sub.b1-326 1175 L.sub.aD-12 L.sub.b1-344 1176 L.sub.aD-12 L.sub.b1-345 1177 L.sub.aD-12 L.sub.b1-346 1178 L.sub.aD-12 L.sub.b1-347 1179 L.sub.aD-12 L.sub.b2-1 1180 L.sub.aD-12 L.sub.b2-2 1181 L.sub.aD-12 L.sub.b2-3 1182 L.sub.aD-12 L.sub.b2-4 1183 L.sub.aD-12 L.sub.b2-5 1184 L.sub.aD-12 L.sub.b2-6 1185 L.sub.aD-12 L.sub.b2-7 1186 L.sub.aD-12 L.sub.b2-8 1187 L.sub.aD-12 L.sub.b2-9 1188 L.sub.aD-12 L.sub.b2-10 1189 L.sub.aD-12 L.sub.b2-11 1190 L.sub.aD-12 L.sub.b2-12 1191 L.sub.aD-12 L.sub.b2-13 1192 L.sub.aD-12 L.sub.b2-14 1193 L.sub.aD-12 L.sub.b2-49 1194 L.sub.aD-12 L.sub.b2-50 1195 L.sub.aD-12 L.sub.b2-51 1196 L.sub.aD-12 L.sub.b2-52 1197 L.sub.aD-12 L.sub.b2-53 1198 L.sub.aD-12 L.sub.b2-54 1199 L.sub.aD-12 L.sub.b2-55 1200 L.sub.aD-12 L.sub.b2-56 1201 L.sub.aD-12 L.sub.b2-57 1202 L.sub.aD-12 L.sub.b2-58 1203 L.sub.aD-12 L.sub.b2-59 1204 L.sub.aD-12 L.sub.b2-60 1205 L.sub.aD-12 L.sub.b2-61 1206 L.sub.aD-12 L.sub.b2-62 1207 L.sub.aD-12 L.sub.b2-63 1208 L.sub.aD-12 L.sub.b2-64 1209 L.sub.aD-12 L.sub.b2-65 1210 L.sub.aD-12 L.sub.b2-66 1211 L.sub.aD-12 L.sub.b2-67 1212 L.sub.aD-12 L.sub.b2-68 1213 L.sub.aD-12 L.sub.b2-69 1214 L.sub.aD-12 L.sub.b2-70 1215 L.sub.aD-12 L.sub.b2-227 1216 L.sub.aD-12 L.sub.b2-228 1217 L.sub.aD-12 L.sub.b2-229 1218 L.sub.aD-12 L.sub.b2-230 1219 L.sub.aD-12 L.sub.b2-231 1220 L.sub.aD-12 L.sub.b2-232 1221 L.sub.aD-12 L.sub.b2-233 1222 L.sub.aD-12 L.sub.b2-234 1223 L.sub.aD-12 L.sub.b2-235 1224 L.sub.aD-12 L.sub.b2-236 1225 L.sub.aD-12 L.sub.b2-237 1226 L.sub.aD-12 L.sub.b2-238 1227 L.sub.aD-12 L.sub.b2-239 1228 L.sub.aD-12 L.sub.b2-240 1229 L.sub.aD-12 L.sub.b2-241 1230 L.sub.aD-12 L.sub.b2-242 1231 L.sub.aD-12 L.sub.b2-243 1232 L.sub.aD-12 L.sub.b2-244 1233 L.sub.aD-12 L.sub.b2-245 1234 L.sub.aD-12 L.sub.b2-246 1235 L.sub.aD-12 L.sub.b2-247 1236 L.sub.aD-12 L.sub.b2-248 1237 L.sub.aD-12 L.sub.b2-249 1238 L.sub.aD-12 L.sub.b2-250 1239 L.sub.aD-12 L.sub.b2-251 1240 L.sub.aD-12 L.sub.b2-252 1241 L.sub.aD-12 L.sub.b2-253 1242 L.sub.aD-12 L.sub.b2-254 1243 L.sub.aD-12 L.sub.b2-255 1244 L.sub.aD-12 L.sub.b2-256 1245 L.sub.aD-12 L.sub.b2-257 1246 L.sub.aD-12 L.sub.b2-258 1247 L.sub.aD-12 L.sub.b2-259 1248 L.sub.aD-12 L.sub.b2-260 1249 L.sub.aD-12 L.sub.b2-261 1250 L.sub.aD-12 L.sub.b2-262 1251 L.sub.aD-12 L.sub.b2-263 1252 L.sub.aD-12 L.sub.b2-264 1253 L.sub.aD-12 L.sub.b2-265 1254 L.sub.aD-12 L.sub.b2-266 1255 L.sub.aD-12 L.sub.b2-267 1256 L.sub.aD-12 L.sub.b2-268 1257 L.sub.aD-12 L.sub.b2-269 1258 L.sub.aD-12 L.sub.b2-270 1259 L.sub.aD-12 L.sub.b2-271 1260 L.sub.aD-12 L.sub.b2-272 1261 L.sub.aD-12 L.sub.b2-273 1262 L.sub.aD-12 L.sub.b2-274 1263 L.sub.aD-12 L.sub.b2-275 1264 L.sub.aD-12 L.sub.bx-1 1265 L.sub.aD-12 L.sub.bx-6 1266 L.sub.aD-12 L.sub.bx-34 1267 L.sub.aD-127 L.sub.b1-1 1268 L.sub.aD-127 L.sub.b1-2 1269 L.sub.aD-127 L.sub.b1-3 1270 L.sub.aD-127 L.sub.b1-4 1271 L.sub.aD-127 L.sub.b1-5 1272 L.sub.aD-127 L.sub.b1-6 1273 L.sub.aD-127 L.sub.b1-7 1274 L.sub.aD-127 L.sub.b1-8 1275 L.sub.aD-127 L.sub.b1-9 1276 L.sub.aD-127 L.sub.b1-10 1277 L.sub.aD-127 L.sub.b1-11 1278 L.sub.aD-127 L.sub.b1-12 1279 L.sub.aD-127 L.sub.b1-13 1280 L.sub.aD-127 L.sub.b1-14 1281 L.sub.aD-127 L.sub.b1-15 1282 L.sub.aD-127 L.sub.b1-16 1283 L.sub.aD-127 L.sub.b1-17 1284 L.sub.aD-127 L.sub.b1-18 1285 L.sub.aD-127 L.sub.b1-45 1286 L.sub.aD-127 L.sub.b1-49 1287 L.sub.aD-127 L.sub.b1-50 1288 L.sub.aD-127 L.sub.b1-57 1289 L.sub.aD-127 L.sub.b1-58 1290 L.sub.aD-127 L.sub.b1-59 1291 L.sub.aD-127 L.sub.b1-60 1292 L.sub.aD-127 L.sub.b1-61 1293 L.sub.aD-127 L.sub.b1-71 1294 L.sub.aD-127 L.sub.b1-72 1295 L.sub.aD-127 L.sub.b1-73 1296 L.sub.aD-127 L.sub.b1-74 1297 L.sub.aD-127 L.sub.b1-75 1298 L.sub.aD-127 L.sub.b1-76 1299 L.sub.aD-127 L.sub.b1-77 1300 L.sub.aD-127 L.sub.b1-78 1301 L.sub.aD-127 L.sub.b1-79 1302 L.sub.aD-127 L.sub.b1-80 1303 L.sub.aD-127 L.sub.b1-81 1304 L.sub.aD-127 L.sub.b1-82 1305 L.sub.aD-127 L.sub.b1-83 1306 L.sub.aD-127 L.sub.b1-84 1307 L.sub.aD-127 L.sub.b1-85 1308 L.sub.aD-127 L.sub.b1-86 1309 L.sub.aD-127 L.sub.b1-87 1310 L.sub.aD-127 L.sub.b1-88 1311 L.sub.aD-127 L.sub.b1-89 1312 L.sub.aD-127 L.sub.b1-90 1313 L.sub.aD-127 L.sub.b1-91 1314 L.sub.aD-127 L.sub.b1-92 1315 L.sub.aD-127 L.sub.b1-93 1316 L.sub.aD-127 L.sub.b1-94 1317 L.sub.aD-127 L.sub.b1-102 1318 L.sub.aD-127 L.sub.b1-103 1319 L.sub.aD-127 L.sub.b1-104 1320 L.sub.aD-127 L.sub.b1-105 1321 L.sub.aD-127 L.sub.b1-106 1322 L.sub.aD-127 L.sub.b1-107 1323 L.sub.aD-127 L.sub.b1-108 1324 L.sub.aD-127 L.sub.b1-109 1325 L.sub.aD-127 L.sub.b1-120 1326 L.sub.aD-127 L.sub.b1-121 1327 L.sub.aD-127 L.sub.b1-122 1328 L.sub.aD-127 L.sub.b1-123 1329 L.sub.aD-127 L.sub.b1-131 1330 L.sub.aD-127 L.sub.b1-132 1331 L.sub.aD-127 L.sub.b1-133 1332 L.sub.aD-127 L.sub.b1-134 1333 L.sub.aD-127 L.sub.b1-135 1334 L.sub.aD-127 L.sub.b1-136 1335 L.sub.aD-127 L.sub.b1-159 1336 L.sub.aD-127 L.sub.b1-160 1337 L.sub.aD-127 L.sub.b1-161 1338 L.sub.aD-127 L.sub.b1-162 1339 L.sub.aD-127 L.sub.b1-163 1340 L.sub.aD-127 L.sub.b1-164 1341 L.sub.aD-127 L.sub.b1-206 1342 L.sub.aD-127 L.sub.b1-207 1343 L.sub.aD-127 L.sub.b1-208 1344 L.sub.aD-127 L.sub.b1-209 1345 L.sub.aD-127 L.sub.b1-210 1346 L.sub.aD-127 L.sub.b1-211 1347 L.sub.aD-127 L.sub.b1-212 1348 L.sub.aD-127 L.sub.b1-213 1349 L.sub.aD-127 L.sub.b1-214 1350 L.sub.aD-127 L.sub.b1-215 1351 L.sub.aD-127 L.sub.b1-216 1352 L.sub.aD-127 L.sub.b1-217 1353 L.sub.aD-127 L.sub.b1-267 1354 L.sub.aD-127 L.sub.b1-268 1355 L.sub.aD-127 L.sub.b1-269 1356 L.sub.aD-127 L.sub.b1-270 1357 L.sub.aD-127 L.sub.b1-273 1358 L.sub.aD-127 L.sub.b1-275 1359 L.sub.aD-127 L.sub.b1-279 1360 L.sub.aD-127 L.sub.b1-280 1361 L.sub.aD-127 L.sub.b1-282 1362 L.sub.aD-127 L.sub.b1-283 1363 L.sub.aD-127 L.sub.b1-284 1364 L.sub.aD-127 L.sub.b1-285 1365 L.sub.aD-127 L.sub.b1-286 1366 L.sub.aD-127 L.sub.b1-287 1367 L.sub.aD-127 L.sub.b1-288 1368 L.sub.aD-127 L.sub.b1-289 1369 L.sub.aD-127 L.sub.b1-290 1370 L.sub.aD-127 L.sub.b1-291 1371 L.sub.aD-127 L.sub.b1-292 1372 L.sub.aD-127 L.sub.b1-293 1373 L.sub.aD-127 L.sub.b1-294 1374 L.sub.aD-127 L.sub.b1-295 1375 L.sub.aD-127 L.sub.b1-299 1376 L.sub.aD-127 L.sub.b1-300 1377 L.sub.aD-127 L.sub.b1-301 1378 L.sub.aD-127 L.sub.b1-302 1379 L.sub.aD-127 L.sub.b1-303 1380 L.sub.aD-127 L.sub.b1-304 1381 L.sub.aD-127 L.sub.b1-305 1382 L.sub.aD-127 L.sub.b1-306 1383 L.sub.aD-127 L.sub.b1-307 1384 L.sub.aD-127 L.sub.b1-308 1385 L.sub.aD-127 L.sub.b1-315 1386 L.sub.aD-127 L.sub.b1-316 1387 L.sub.aD-127 L.sub.b1-317 1388 L.sub.aD-127 L.sub.b1-318 1389 L.sub.aD-127 L.sub.b1-319 1390 L.sub.aD-127 L.sub.b1-320 1391 L.sub.aD-127 L.sub.b1-321 1392 L.sub.aD-127 L.sub.b1-322 1393 L.sub.aD-127 L.sub.b1-323 1394 L.sub.aD-127 L.sub.b1-324 1395 L.sub.aD-127 L.sub.b1-325 1396 L.sub.aD-127 L.sub.b1-326 1397 L.sub.aD-127 L.sub.b1-344 1398 L.sub.aD-127 L.sub.b1-345 1399 L.sub.aD-127 L.sub.b1-346 1400 L.sub.aD-127 L.sub.b1-347 1401 L.sub.aD-127 L.sub.b2-1 1402 L.sub.aD-127 L.sub.b2-2 1403 L.sub.aD-127 L.sub.b2-3 1404 L.sub.aD-127 L.sub.b2-4 1405 L.sub.aD-127 L.sub.b2-5 1406 L.sub.aD-127 L.sub.b2-6 1407 L.sub.aD-127 L.sub.b2-7 1408 L.sub.aD-127 L.sub.b2-8 1409 L.sub.aD-127 L.sub.b2-9 1410 L.sub.aD-127 L.sub.b2-10 1411 L.sub.aD-127 L.sub.b2-11 1412 L.sub.aD-127 L.sub.b2-12 1413 L.sub.aD-127 L.sub.b2-13 1414 L.sub.aD-127 L.sub.b2-14 1415 L.sub.aD-127 L.sub.b2-49 1416 L.sub.aD-127 L.sub.b2-50 1417 L.sub.aD-127 L.sub.b2-51 1418 L.sub.aD-127 L.sub.b2-52 1419 L.sub.aD-127 L.sub.b2-53 1420 L.sub.aD-127 L.sub.b2-54 1421 L.sub.aD-127 L.sub.b2-55 1422 L.sub.aD-127 L.sub.b2-56 1423 L.sub.aD-127 L.sub.b2-57 1424 L.sub.aD-127 L.sub.b2-58 1425 L.sub.aD-127 L.sub.b2-59 1426 L.sub.aD-127 L.sub.b2-60 1427 L.sub.aD-127 L.sub.b2-61 1428 L.sub.aD-127 L.sub.b2-62 1429 L.sub.aD-127 L.sub.b2-63 1430 L.sub.aD-127 L.sub.b2-64 1431 L.sub.aD-127 L.sub.b2-65 1432 L.sub.aD-127 L.sub.b2-66 1433 L.sub.aD-127 L.sub.b2-67 1434 L.sub.aD-127 L.sub.b2-68 1435 L.sub.aD-127 L.sub.b2-69 1436 L.sub.aD-127 L.sub.b2-70 1437 L.sub.aD-127 L.sub.b2-227 1438 L.sub.aD-127 L.sub.b2-228 1439 L.sub.aD-127 L.sub.b2-229 1440 L.sub.aD-127 L.sub.b2-230 1441 L.sub.aD-127 L.sub.b2-231 1442 L.sub.aD-127 L.sub.b2-232 1443 L.sub.aD-127 L.sub.b2-233 1444 L.sub.aD-127 L.sub.b2-234 1445 L.sub.aD-127 L.sub.b2-235 1446 L.sub.aD-127 L.sub.b2-236 1447 L.sub.aD-127 L.sub.b2-237 1448 L.sub.aD-127 L.sub.b2-238 1449 L.sub.aD-127 L.sub.b2-239 1450 L.sub.aD-127 L.sub.b2-240 1451 L.sub.aD-127 L.sub.b2-241 1452 L.sub.aD-127 L.sub.b2-242 1453 L.sub.aD-127 L.sub.b2-243 1454 L.sub.aD-127 L.sub.b2-244 1455 L.sub.aD-127 L.sub.b2-245 1456 L.sub.aD-127 L.sub.b2-246 1457 L.sub.aD-127 L.sub.b2-247 1458 L.sub.aD-127 L.sub.b2-248 1459 L.sub.aD-127 L.sub.b2-249 1460 L.sub.aD-127 L.sub.b2-250 1461 L.sub.aD-127 L.sub.b2-251 1462 L.sub.aD-127 L.sub.b2-252 1463 L.sub.aD-127 L.sub.b2-253 1464 L.sub.aD-127 L.sub.b2-254 1465 L.sub.aD-127 L.sub.b2-255 1466 L.sub.aD-127 L.sub.b2-256 1467 L.sub.aD-127 L.sub.b2-257 1468 L.sub.aD-127 L.sub.b2-258 1469 L.sub.aD-127 L.sub.b2-259 1470 L.sub.aD-127 L.sub.b2-260 1471 L.sub.aD-127 L.sub.b2-261 1472 L.sub.aD-127 L.sub.b2-262 1473 L.sub.aD-127 L.sub.b2-263 1474 L.sub.aD-127 L.sub.b2-264 1475 L.sub.aD-127 L.sub.b2-265 1476 L.sub.aD-127 L.sub.b2-266 1477 L.sub.aD-127 L.sub.b2-267 1478 L.sub.aD-127 L.sub.b2-268 1479 L.sub.aD-127 L.sub.b2-269 1480 L.sub.aD-127 L.sub.b2-270 1481 L.sub.aD-127 L.sub.b2-271 1482 L.sub.aD-127 L.sub.b2-272 1483 L.sub.aD-127 L.sub.b2-273 1484 L.sub.aD-127 L.sub.b2-274 1485 L.sub.aD-127 L.sub.b2-275 1486 L.sub.aD-127 L.sub.bx-1 1487 L.sub.aD-127 L.sub.bx-6 1488 L.sub.aD-127 L.sub.bx-34 1489 L.sub.a1-13 L.sub.b1-356 1490 L.sub.a1-13 L.sub.b1-357 1491 L.sub.a1-13 L.sub.b2-284 1492 L.sub.a1-13 L.sub.b2-285 1493 L.sub.a1-122 L.sub.b1-1 1494 L.sub.a1-122 L.sub.b1-75 1495 L.sub.a1-122 L.sub.b1-282 1496 L.sub.a1-122 L.sub.b1-345 1497 L.sub.a1-122 L.sub.b2-49 1498 L.sub.a1-122 L.sub.b2-192 1499 L.sub.a1-123 L.sub.b1-1 1500 L.sub.a1-123 L.sub.b1-75 1501 L.sub.a1-123 L.sub.b1-282 1502 L.sub.a1-123 L.sub.b1-345 1503 L.sub.a1-123 L.sub.b2-49 1504 L.sub.a1-123 L.sub.b2-192
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, at least one of the first host compound and 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
[0034]
[0035]
DETAILED DESCRIPTION
[0036] OLEDs can be fabricated on various types of substrates such as glass, plastic, and metal foil.
[0037] 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.
[0038] 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.
[0039] 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.
[0040] An OLED can be encapsulated by a barrier layer.
[0041] 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.
[0042] The materials and structures described herein may be used in other organic electronic devices listed above.
[0043] 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.
[0044] 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.
[0045] 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.
[0046] 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).
[0047] 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.
[0048] 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 (AES-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.
[0049] Definition of Terms of Substituents
[0050] Halogen or halide—as used herein includes fluorine, chlorine, bromine, and iodine.
[0051] 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.
[0052] 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.
[0053] 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.
[0054] 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.
[0055] 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.
[0056] 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.
[0057] 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.
[0058] 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.
[0059] 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.
[0060] 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.
[0061] 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.
[0062] 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.
[0063] 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.
[0064] Alkylgermanyl—as used herein contemplates a 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.
[0065] 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.
[0066] 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.
[0067] In the present disclosure, unless otherwise defined, when any term of the group consisting of substituted alkyl, substituted cycloalkyl, substituted heteroalkyl, substituted heterocyclic group, substituted arylalkyl, substituted alkoxy, substituted aryloxy, substituted alkenyl, substituted alkynyl, substituted aryl, substituted heteroaryl, substituted alkylsilyl, substituted arylsilyl, substituted alkylgermanyl, substituted arylgermanyl, substituted amino, substituted acyl, substituted carbonyl, a substituted carboxylic acid group, a substituted ester group, substituted sulfinyl, substituted sulfonyl, and substituted phosphino is used, it means that any group of alkyl, cycloalkyl, heteroalkyl, heterocyclic group, arylalkyl, alkoxy, aryloxy, alkenyl, alkynyl, aryl, heteroaryl, alkylsilyl, arylsilyl, amino, acyl, carbonyl, a carboxylic acid group, an ester group, sulfinyl, sulfonyl, and phosphino may be substituted with one or more moieties selected from the group consisting of deuterium, halogen, unsubstituted alkyl having 1 to 20 carbon atoms, unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, unsubstituted heteroalkyl having 1 to 20 carbon atoms, an unsubstituted heterocyclic group having 3 to 20 ring atoms, unsubstituted arylalkyl having 7 to 30 carbon atoms, unsubstituted alkoxy having 1 to 20 carbon atoms, unsubstituted aryloxy having 6 to 30 carbon atoms, unsubstituted alkenyl having 2 to 20 carbon atoms, unsubstituted alkynyl having 2 to 20 carbon atoms, unsubstituted aryl having 6 to 30 carbon atoms, unsubstituted heteroaryl having 3 to 30 carbon atoms, unsubstituted alkylsilyl having 3 to 20 carbon atoms, unsubstituted arylsilyl group having 6 to 20 carbon atoms, unsubstituted alkylgermanyl having 3 to 20 carbon atoms, unsubstituted arylgermanyl having 6 to 20 carbon atoms, unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof.
[0068] 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.
[0069] In the compounds mentioned in the present disclosure, hydrogen atoms may be partially or fully replaced by deuterium. Other atoms such as carbon and nitrogen may also be replaced by their other stable isotopes. The replacement by other stable isotopes in the compounds may be preferred due to its enhancements of device efficiency and stability.
[0070] In the compounds mentioned in the present disclosure, multiple substitution refers to a range that includes a di-substitution, up to the maximum available substitution. When substitution in the compounds mentioned in the present disclosure represents multiple substitution (including di-, tri-, and tetra-substitutions etc.), that means the substituent may exist at a plurality of available substitution positions on its linking structure, the substituents present at a plurality of available substitution positions may have the same structure or different structures.
[0071] 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, fusedcyclic, 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.
[0072] 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:
##STR00005##
[0073] 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:
##STR00006##
[0074] 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:
##STR00007##
[0075] 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:
##STR00008##
[0076] 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;
[0077] wherein
[0078] 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 tetradentate ligand or a multidentate ligand;
[0079] the metal M is selected from a metal with a relative atomic mass greater than 40; and
[0080] 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 may be identical or different; when n is 2, two L.sub.b may be identical or different;
[0081] wherein 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:
##STR00009##
[0082] wherein
[0083] Z is, at each occurrence identically or differently, selected from the group consisting of O, S, Se, NR′, CR′R′ and SiR′R′; when two R′ are present at the same time, the two R′ are identical or different;
[0084] Cy is, at each occurrence identically or differently, selected from a substituted or unsubstituted aromatic ring having 6 to 24 ring atoms, a substituted or unsubstituted heteroaromatic ring having 5 to 24 ring atoms or a combination thereof;
[0085] X.sub.1 to X.sub.8 are, at each occurrence identically or differently, selected from C, CR.sub.x or N, and at least one of X.sub.1 to X.sub.4 is selected from C and joined to Cy;
[0086] at least one of X.sub.1 to X.sub.8 is selected from CR.sub.x, and the R.sub.x is cyano or fluorine;
[0087] X.sub.1, X.sub.2, X.sub.3 or X.sub.4 is joined to the metal M by a metal-carbon bond or a metal-nitrogen bond;
[0088] U.sub.1 to U.sub.4 are, at each occurrence identically or differently, selected from CR.sub.u or N; and
[0089] W.sub.1 to W.sub.3 are, at each occurrence identically or differently, selected from CR.sub.w or N;
[0090] wherein in Formula 1A, R.sub.A has a structure represented by Formula 2, and the total number of carbon atoms in Formula 2 is greater than or equal to 2:
##STR00010##
[0091] wherein “*” represents a position where Formula 2 is joined to Formula 1A;
[0092] R.sub.A1, R.sub.A2, R.sub.A3, R′, R.sub.x, R.sub.u and R.sub.w 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;
[0093] adjacent substituents R.sub.A1, R.sub.A2, R.sub.A3, R′, R.sub.x, R.sub.u, R.sub.w can be optionally joined to form a ring; and
[0094] L.sub.c is a monoanionic bidentate ligand.
[0095] In the present disclosure, the expression “adjacent substituents R.sub.A1, R.sub.A2, R.sub.A3, R′, R.sub.x, R.sub.u, R.sub.w 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.A1 and R.sub.A2, substituents R.sub.A1 and R.sub.A3, substituents R.sub.A2 and R.sub.A3, substituents R.sub.A1 and R.sub.u, substituents R.sub.u and R.sub.A3, substituents R.sub.A2 and R.sub.u, two substituents R′, substituents R′ and R.sub.x, two substituents R.sub.x, two substituents R.sub.u, and two substituents R.sub.w, can be joined to form a ring. Obviously, it is possible that none of these substituents are joined to form a ring.
[0096] According to an embodiment of the present disclosure, L.sub.c is, at each occurrence identically or differently, selected from a structure represent by any one of the group consisting of the following:
##STR00011##
[0097] wherein
[0098] R.sub.a, R.sub.b and R.sub.c represent, at each occurrence identically or differently, mono-substitution, multiple substitutions or non-substitution;
[0099] 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;
[0100] 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
[0101] adjacent substituents R.sub.a, R.sub.b, R.sub.c, R.sub.N1, R.sub.C1 and R.sub.C2 can be optionally joined to form a ring.
[0102] In the present disclosure, the expression that “adjacent substituents R.sub.a, R.sub.b, R.sub.c, R.sub.N1, R.sub.C1 and R.sub.C2 can be optionally joined to form a ring” is intended to mean that any one or more of groups of adjacent substituents, such as two substituents R.sub.a, two substituents R.sub.b, two substituents R.sub.c, 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.
[0103] According to an embodiment of the present disclosure, Cy is selected from any structure of the group consisting of the following:
##STR00012##
[0104] wherein
[0105] R represents, at each occurrence identically or differently, mono-substitution, multiple substitutions or non-substitution; and when multiple R are present at the same time in any structure, the multiple R are the same or different;
[0106] R is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof;
[0107] adjacent substituents R can be optionally joined to form a ring; and
[0108] “#” represents a position where Cy is joined to the metal M, and “
##STR00013##
” represents a position where Cy is joined to X.sub.1, X.sub.2, X.sub.3 or X.sub.4.
[0109] In the present disclosure, the expression that “adjacent substituents R can be optionally joined to form a ring” is intended to mean that any one or more of groups of any two adjacent substituents R can be joined to form a ring. Obviously, it is possible that none of these substituents are joined to form a ring.
[0110] According to an embodiment of the present disclosure, L.sub.b has a structure represented by any of Formulas 1Ba to 1Bf:
##STR00014## ##STR00015##
[0111] wherein
[0112] Z is, at each occurrence identically or differently, selected from the group consisting of O, S, Se, NR′, CR′R′ and SiR′R′; when two R′ are present at the same time, the two R′ are identical or different;
[0113] in Formulas 1Ba and 1Bf, X.sub.3 to X.sub.8 are, at each occurrence identically or differently, selected from CR.sub.x or N;
[0114] in Formulas 1Bb and 1Bd, X.sub.1 and X.sub.4 to X.sub.8 are, at each occurrence identically or differently, selected from CR.sub.x or N;
[0115] in Formulas 1Bc and 1Be, X.sub.1 and X.sub.2 and X.sub.5 to X.sub.8 are, at each occurrence identically or differently, selected from CR.sub.x or N;
[0116] at least one of X.sub.1 to X.sub.8 is selected from CR.sub.x, and the R.sub.x is cyano or fluorine;
[0117] Y.sub.1 to Y.sub.4 are, at each occurrence identically or differently, selected from CR.sub.y or N;
[0118] R′, 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
[0119] adjacent substituents R′, R.sub.x, R.sub.y can be optionally joined to form a ring.
[0120] In this embodiment, the expression that “adjacent substituents R′, R.sub.x, 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′, two substituents R.sub.x, two substituents R.sub.y, and substituents R′ and R.sub.x, can be joined to form a ring. Obviously, it is possible that none of these substituents are joined to form a ring.
[0121] According to an embodiment of the present disclosure, the metal M is, at each occurrence identically or differently, selected from the group consisting of Cu, Ag, Au, Ru, Rh, Pd, Os, Ir and Pt.
[0122] According to an embodiment of the present disclosure, the metal M is, at each occurrence identically or differently, selected from Pt or Jr.
[0123] According to an embodiment of the present disclosure, a metal complex Ir(L.sub.a).sub.m(L.sub.b).sub.3−m has a structure represented by Formula 3:
##STR00016##
[0124] wherein
[0125] Z is, at each occurrence identically or differently, selected from the group consisting of O, S, Se, NR′, CR′R′ and SiR′R′; when two R′ are present at the same time, the two R′ are identical or different;
[0126] X.sub.3 to X.sub.8 are, at each occurrence identically or differently, selected from CR.sub.x or N;
[0127] at least one of X.sub.3 to X.sub.8 is selected from CR.sub.x, and the R.sub.x is cyano or fluorine;
[0128] Y.sub.1 to Y.sub.4 are, at each occurrence identically or differently, selected from CR.sub.y or N;
[0129] U.sub.1 to U.sub.4 are, at each occurrence identically or differently, selected from CR.sub.u or N;
[0130] W.sub.1 to W.sub.3 are, at each occurrence identically or differently, selected from CRv or N;
[0131] R.sub.A1, R.sub.A2, R.sub.A3, R′, R.sub.x, R.sub.y, R.sub.u and R.sub.w 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 the total number of carbon atoms in R.sub.A1, R.sub.A2 and R.sub.A3 is greater than or equal to 1;
[0132] adjacent substituents R.sub.A1, R.sub.A2, R.sub.A3 can be optionally joined to form a ring; and
[0133] adjacent substituents R′, R.sub.x, R.sub.y, R.sub.u, R.sub.w can be optionally joined to form a ring.
[0134] In the present disclosure, the expression that “adjacent substituents R.sub.A1, R.sub.A2, R.sub.A3 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.A1 and R.sub.A2, substituents R.sub.A1 and R.sub.A3, and substituents R.sub.A2 and R.sub.A3, can be joined to form a ring. Obviously, it is possible that none of these substituents are joined to form a ring.
[0135] In the present disclosure, the expression that “adjacent substituents R′, R.sub.x, R.sub.y, R.sub.u, R.sub.wcan 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′, substituents R′ and R.sub.x, two substituents R.sub.x, two substituents R.sub.u, two substituents R.sub.w, and two substituents 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, the metal complex Ir(L.sub.a).sub.m(L.sub.b).sub.3−m has a structure represented by Formula 4 or Formula 5:
##STR00017##
[0137] wherein
[0138] R.sub.x and R.sub.y represent, at each occurrence identically or differently, mono-substitution, multiple substitutions or non-substitution;
[0139] R.sub.A1, R.sub.A2, R.sub.A3, R.sub.x, R.sub.y and R.sub.1 to R.sub.7 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 the total number of carbon atoms in R.sub.A1, R.sub.A2 and R.sub.A3 is greater than or equal to 1;
[0140] at least one R.sub.x is cyano or fluorine;
[0141] adjacent substituents R.sub.A1, R.sub.A2, R.sub.A3 can be optionally joined to form a ring; and
[0142] adjacent substituents R.sub.x, R.sub.y, R.sub.1 to R.sub.7 can be optionally joined to form a ring.
[0143] In the present disclosure, the expression that “adjacent substituents R.sub.x, R.sub.y, R.sub.1 to R.sub.7 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.1 and R.sub.2, substituents R.sub.3 and R.sub.4, substituents R.sub.4 and R.sub.5, substituents R.sub.5 and R.sub.6, substituents R.sub.6 and R.sub.7, two substituents R.sub.x, and two substituents 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.
[0144] According to an embodiment of the present disclosure, Z is selected from the group consisting of: O and S.
[0145] According to an embodiment of the present disclosure, Z is selected from O.
[0146] According to an embodiment of the present disclosure, X.sub.1 to X.sub.8 are, at each occurrence identically or differently, selected from C or CR.sub.x.
[0147] According to an embodiment of the present disclosure, X.sub.3 to X.sub.8 are, at each occurrence identically or differently, selected from C or CR.sub.x.
[0148] According to an embodiment of the present disclosure, at least one of X.sub.1 to X.sub.8 is selected from N. For example, one of X.sub.1 to X.sub.8 is selected from N, or two of X.sub.1 to X.sub.8 are selected from N.
[0149] 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.
[0150] According to an embodiment of the present disclosure, W.sub.1 to W.sub.3 are, at each occurrence identically or differently, selected from C or CR.sub.w.
[0151] According to an embodiment of the present disclosure, U.sub.1 to U.sub.4 are, at each occurrence identically or differently, selected from C or CR.sub.u.
[0152] According to an embodiment of the present disclosure, Y.sub.1 to Y.sub.4 are, at each occurrence identically or differently, selected from C or CR.sub.y.
[0153] According to an embodiment of the present disclosure, at least one of W.sub.1 to W.sub.3 is selected from N. For example, one of W.sub.1 to W.sub.3 is selected from N, or two of W.sub.1 to W.sub.3 are selected from N.
[0154] According to an embodiment of the present disclosure, at least one of U.sub.1 to U.sub.4 is selected from N. For example, one of U.sub.1 to U.sub.4 is selected from N, or two of U.sub.1 to U.sub.4 are selected from N.
[0155] 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.
[0156] According to an embodiment of the present disclosure, R.sub.w 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 aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms and combinations thereof.
[0157] According to an embodiment of the present disclosure, R.sub.w and R.sub.u 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.
[0158] According to an embodiment of the present disclosure, R.sub.w and R.sub.u 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.
[0159] 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.
[0160] 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.
[0161] 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.
[0162] According to an embodiment of the present disclosure, U.sub.1 to U.sub.4 are, at each occurrence identically or differently, selected from CR.sub.u, and the total number of carbon atoms in R.sub.u is at least 4.
[0163] According to an embodiment of the present disclosure, at least one of U.sub.1 to U.sub.4 is selected from CR.sub.u, and the R.sub.u is 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 and combinations thereof.
[0164] According to an embodiment of the present disclosure, the total number of carbon atoms in all R.sub.u is at least 4.
[0165] According to an embodiment of the present disclosure, at least one of U.sub.1 to U.sub.4 is selected from CR.sub.u, and the R.sub.u is selected from the group consisting of: substituted or unsubstituted alkyl having 1 to 12 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 12 ring carbon atoms and combinations thereof.
[0166] According to an embodiment of the present disclosure, U.sub.2 and/or U.sub.3 is selected from CR.sub.u, and the R.sub.u is selected from the group consisting of: substituted or unsubstituted alkyl having 1 to 12 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 12 ring carbon atoms and combinations thereof, and the total number of carbon atoms in all R.sub.u is at least 4.
[0167] According to an embodiment of the present disclosure, U.sub.2 or U.sub.3 is selected from CR.sub.u, and the R.sub.u is selected from substituted or unsubstituted alkyl having 3 to 12 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 12 ring carbon atoms or a combination thereof.
[0168] According to an embodiment of the present disclosure, U.sub.2 or U.sub.3 is selected from CR.sub.u, and the R.sub.u is selected from substituted or unsubstituted alkyl having 4 to 12 carbon atoms, substituted or unsubstituted cycloalkyl having 4 to 12 ring carbon atoms or a combination thereof.
[0169] According to an embodiment of the present disclosure, at least one of U.sub.1 to U.sub.4 is selected from CR.sub.1, and the R.sub.u is selected from the group consisting of: substituted or unsubstituted alkyl having 3 to 12 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 12 ring carbon atoms and combinations thereof.
[0170] According to an embodiment of the present disclosure, at least one of U.sub.1 to U.sub.4 is selected from CR.sub.1, and the R.sub.u has a structure represented by Formula 2.
[0171] According to an embodiment of the present disclosure, U.sub.2 or U.sub.3 is selected from CR.sub.u, and the R.sub.u has a structure represented by Formula 2.
[0172] According to an embodiment of the present disclosure, R.sub.A1, R.sub.A2 and R.sub.A3 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 the total number of carbon atoms in R.sub.A1, R.sub.A2 and R.sub.A3 is greater than or equal to 3.
[0173] According to an embodiment of the present disclosure, the total number of carbon atoms in Formula 2 is greater than or equal to 4.
[0174] According to an embodiment of the present disclosure, R.sub.A1, R.sub.A2 and R.sub.A3 are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 6 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 6 ring atoms, substituted or unsubstituted arylalkyl having 7 to 13 carbon atoms, substituted or unsubstituted aryl having 6 to 12 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 12 carbon atoms, a cyano group and combinations thereof, and the total number of carbon atoms in R.sub.A1, R.sub.A2 and R.sub.A3 is greater than or equal to 3.
[0175] According to an embodiment of the present disclosure, R.sub.A1, R.sub.A2 and R.sub.A3 are, at each occurrence identically or differently, selected from the group consisting of: substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms, substituted or unsubstituted aryl having 6 to 12 carbon atoms and combinations thereof.
[0176] According to an embodiment of the present disclosure, R.sub.A1, R.sub.A2 and R.sub.A3 are, at each occurrence identically or differently, selected from the group consisting of: substituted or unsubstituted alkyl having 1 to 6 carbon atoms or substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms; and the total number of carbon atoms in R.sub.A1, R.sub.A2 and R.sub.A3 is greater than or equal to 3 and less than or equal to 9.
[0177] According to an embodiment of the present disclosure, two of R.sub.A1, R.sub.A2 and R.sub.A3 are, identically or differently, selected from the group consisting of: substituted or unsubstituted alkyl having 1 to 6 carbon atoms or substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms; and another one of R.sub.A1, R.sub.A2 and R.sub.A3 is selected from the group consisting of: deuterium, fluorine, 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, a cyano group and combinations thereof.
[0178] According to an embodiment of the present disclosure, two of R.sub.A1, R.sub.A2 and R.sub.A3 are, identically or differently, selected from the group consisting of: substituted or unsubstituted alkyl having 1 to 6 carbon atoms or substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms; and another one of R.sub.A1, R.sub.A2 and R.sub.A3 is selected from the group consisting of: deuterium, fluorine, substituted or unsubstituted aryl having 6 to 18 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 18 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 12 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 12 carbon atoms, a cyano group and combinations thereof.
[0179] According to an embodiment of the present disclosure, Formula 2 is, at each occurrence identically or differently, selected from the group consisting of A-1 to A-83, wherein the specific structures of A-1 to A-83 are referred to claim 14.
[0180] According to an embodiment of the present disclosure, hydrogen in A-1 to A-83 can be partially or fully substituted with deuterium.
[0181] According to an embodiment of the present disclosure, at least one of X.sub.1 to X.sub.8 is selected from CR.sub.x, and the R.sub.x is cyano or fluorine.
[0182] 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 the R.sub.x is cyano or fluorine.
[0183] 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 the R.sub.x is cyano or fluorine.
[0184] According to an embodiment of the present disclosure, at least one of X.sub.7 or X.sub.8 is selected from CR.sub.x, and the R.sub.x is cyano or fluorine.
[0185] According to an embodiment of the present disclosure, X.sub.8 is selected from CR.sub.x.
[0186] According to an embodiment of the present disclosure, when X.sub.8 is selected from N, at least one of X.sub.1 to X.sub.7 is selected from CR.sub.x, and the R.sub.x is cyano; when the rest of X.sub.1 to X.sub.7 is(are) selected from CR.sub.x, R.sub.x is selected from hydrogen, deuterium, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, a cyano group and combinations thereof.
[0187] According to an embodiment of the present disclosure, at least two of X.sub.3 to X.sub.8 are CR.sub.x, one R.sub.x is 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 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.
[0188] According to an embodiment of the present disclosure, at least two of X.sub.5 to X.sub.8 are CR.sub.x, one R.sub.x is 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.
[0189] According to an embodiment of the present disclosure, X.sub.7 and X.sub.8 are selected from CR.sub.x, 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 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms, substituted or unsubstituted aryl having 6 to 12 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 12 carbon atoms and combinations thereof.
[0190] 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 alkylgermanyl 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.
[0191] 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 and combinations thereof.
[0192] According to an embodiment of the present disclosure, R′ is, at each occurrence identically or differently, selected from substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms, substituted or unsubstituted aryl having 6 to 12 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 12 carbon atoms or a combination thereof.
[0193] According to an embodiment of the present disclosure, R′ is selected from methyl, phenyl or deuterated methyl.
[0194] 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.a1−121, L.sub.a2−1 to L.sub.a2−116 and L.sub.aD−1 to L.sub.aD−128, wherein the specific structures of L.sub.a1−1 to L.sub.a1−121, L.sub.a2−1 to L.sub.a2−116 and L.sub.aD−1 to L.sub.aD−128 are referred to claim 17.
[0195] According to an embodiment of the present disclosure, hydrogen in L.sub.a1−1 to L.sub.a1−121, L.sub.a2−1 to L.sub.a2−116 and L.sub.aD−1 to L.sub.aD−128 can be partially or fully substituted with deuterium.
[0196] 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.b2−283 and L.sub.bx−1 to L.sub.bx−76, wherein the specific structures of L.sub.b1−1 to L.sub.b1−355, L.sub.b2−1 to L.sub.b2−283 and L.sub.bx−1 to L.sub.bx−76 are referred to claim 18.
[0197] According to an embodiment of the present disclosure, hydrogen in L.sub.b1−1 to L.sub.b1−355, L.sub.b2−1 to L.sub.b2−283 and L.sub.bx−1 to L.sub.bx−76 can be partially or fully substituted with deuterium.
[0198] 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.
[0199] 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.a1−121, L.sub.a2−1 to L.sub.a2−116 and L.sub.aD−1 to L.sub.aD−128, 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.b2−283 and L.sub.bx−1 to L.sub.bx−76.
[0200] 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.a1−121, L.sub.a2−1 to L.sub.a2−116 and L.sub.aD−1 to L.sub.aD−128, 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.b2−283 and L.sub.bx−1 to L.sub.bx−76.
[0201] 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.a1−121, L.sub.a2−1 to L.sub.a2−116 and L.sub.aD−1 to L.sub.aD−128, 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.b2−283 and L.sub.bx−1 to L.sub.bx−76, and L.sub.c is selected from the group consisting of L.sub.c1to 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 is selected from the group consisting of Metal Complex 1 to Metal Complex 1488, wherein the specific structures of Metal Complex 1 to Metal Complex 1488 are referred to claim 20.
[0203] 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.a1−123, L.sub.a2−1 to L.sub.a2−116 and L.sub.aD−1 to L.sub.aD−128, wherein the specific structures of L.sub.a1−1 to L.sub.a1−123, L.sub.a2−1 to L.sub.a2−116 and L.sub.aD−1 to L.sub.aD−128 are referred to claim 17.
[0204] According to an embodiment of the present disclosure, hydrogen in L.sub.a1−1 to L.sub.a1−123, L.sub.a2−1 to L.sub.a2−116 and L.sub.aD−1 to L.sub.aD−128 can be partially or fully substituted with deuterium.
[0205] 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.b1−357, L.sub.b2−1 to L.sub.b2−285 and L.sub.bx−1 to L.sub.bx−76, wherein the specific structures of L.sub.b1−1 to L.sub.b1−357, L.sub.b2−1 to L.sub.b2−285 and L.sub.bx−1 to L.sub.bx−76 are referred to claim 18.
[0206] According to an embodiment of the present disclosure, hydrogen in L.sub.b1−1 to L.sub.b1−357, L.sub.b2−1 to L.sub.b2−285 and L.sub.bx−1 to L.sub.bx−76 can be partially or fully substituted with deuterium.
[0207] 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.
[0208] 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.a1−123, L.sub.a2−1 to L.sub.a2−116 and L.sub.aD−1 to L.sub.aD−128, and L.sub.b is selected from the group consisting of L.sub.b1−1 to L.sub.b1−357, L.sub.b2−1 to L.sub.b2−285 and L.sub.bx−1 to L.sub.bx−76.
[0209] 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.a1−123, L.sub.a2−1 to L.sub.a2−116 and L.sub.aD−1 to L.sub.aD−128, and L.sub.b is, at each occurrence identically or differently, selected from the group consisting of L.sub.b1−1 to L.sub.b1−357, L.sub.b2−1 to L.sub.b2−285 and L.sub.bx−1 to L.sub.bx−76.
[0210] 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.a1−123, L.sub.a2−1 to L.sub.a2−116 and L.sub.aD−1 to L.sub.aD−128, L.sub.b is selected from the group consisting of L.sub.b1−1 to L.sub.b1−357, L.sub.b2−1 to L.sub.b2−285 and L.sub.bx−1 to L.sub.bx−76, and L.sub.c is 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.
[0211] According to an embodiment of the present disclosure, the metal complex is selected from the group consisting of Metal Complex 1 to Metal Complex 1504, wherein the specific structures of Metal Complex 1 to Metal Complex 1504 are referred to claim 20.
[0212] According to an embodiment of the present disclosure, further disclosed is an electroluminescent device including:
[0213] an anode,
[0214] a cathode, and
[0215] 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.
[0216] According to an embodiment of the present disclosure, the organic layer comprising the metal complex in the electroluminescent device is an emissive layer.
[0217] According to an embodiment of the present disclosure, the electroluminescent device emits green light.
[0218] According to an embodiment of the present disclosure, the electroluminescent device emits white light.
[0219] According to an embodiment of the present disclosure, the emissive layer of the electroluminescent device further comprises a first host compound.
[0220] According to an embodiment of the present disclosure, the emissive layer of the electroluminescent device further comprises a first host compound and at least one second host compound.
[0221] According to an embodiment of the present disclosure, at least one of the first host compound and 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.
[0222] According to an embodiment of the present disclosure, the first host compound in the electroluminescent device has a structure represented by Formula X:
##STR00018##
[0223] wherein
[0224] 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;
[0225] 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;
[0226] 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;
[0227] 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;
[0228] 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;
[0229] adjacent substituents R.sub.v and R.sub.t can be optionally joined to form a ring.
[0230] 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.
[0231] 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:
##STR00019## ##STR00020##
[0232] wherein
[0233] 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;
[0234] V is, at each occurrence identically or differently, selected from CR.sub.v or N;
[0235] T is, at each occurrence identically or differently, selected from CR.sub.t or N;
[0236] 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;
[0237] 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;
[0238] adjacent substituents R.sub.v and R.sub.t can be optionally joined to form a ring.
[0239] 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.
[0240] 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.
[0241] 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.
[0242] Combination with Other Materials
[0243] 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.
[0244] 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.
[0245] 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.
Material Synthesis Example
[0246] The method for preparing a compound in the present disclosure is not limited herein. Typically, the following compounds are used as examples without limitations, and synthesis routes and preparation methods thereof are described below.
Synthesis Example 1: Synthesis of Metal Complex 241
[0247] Step 1:
##STR00021##
[0248] 2-(3-t-butylphenyl)-pyridine (3.6 g, 17.1 mmol), iridium trichloride trihydrate (1.6 g, 4.5 mmol), 120 mL of 2-ethoxyethanol and 40 mL of water were sequentially added to a dry 500 mL round-bottom flask, purged with nitrogen three times, and heated and stirred for 24 h at 130° C. under nitrogen protection. The solution was cooled, filtered, washed three times with methanol and n-hexane respectively, and suction-filtrated to dryness to obtain 2.8 g of Intermediate 1 (with a yield of 96%).
[0249] Step 2:
##STR00022##
[0250] Intermediate 1 (2.8 g, 2.2 mmol), 100 mL of anhydrous dichloromethane, 10 mL of methanol and silver trifluoromethanesulfonate (1.2 g, 4.8 mmol) were sequentially added to a dry 250 mL round-bottom flask, purged with nitrogen three times, and stirred overnight at room temperature under nitrogen protection. The solution was filtered through Celite and washed twice with dichloromethane. The organic phases below were collected and concentrated under reduced pressure to obtain 3.6 g of Intermediate 2 as a yellow solid (with a yield of 99%).
[0251] Step 3:
##STR00023##
[0252] Intermediate 2 (3.6 g, 4.4 mmol), Intermediate 3 (1.8 g, 6.6 mmol), 2-ethoxyethanol (50 mL) and DMF (50 mL) were sequentially added into a dry 250 mL round-bottom flask and heated to react for 96 h at 100° C. 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 241 as a yellow solid (2.8 g with a yield of 72%). The product structure was confirmed as the target product with a molecular weight of 883.3.
Synthesis Example 2: Synthesis of Metal Complex 13
[0253] Step 1:
##STR00024##
[0254] 5-t-butyl-2-(3-t-butylphenyl)-pyridine (4.7 g, 17.6 mmol), iridium trichloride trihydrate (1.5 g, 4.2 mmol), 120 mL of 2-ethoxyethanol and 40 mL of water were sequentially added to a dry 500 mL round-bottom flask, purged with nitrogen three times, and heated and stirred for 24 h at 130° C. under nitrogen protection. The solution was cooled, filtered, washed three times with methanol and n-hexane respectively, and suction-filtrated to dryness to obtain 3.0 g of Intermediate 4 (with a yield of 96%).
[0255] Step 2:
##STR00025##
[0256] Intermediate 4 (3.0 g, 2.0 mmol), 100 mL of anhydrous dichloromethane, 10 mL of methanol and silver trifluoromethanesulfonate (1.1 g, 4.3 mmol) were sequentially added to a dry 250 mL round-bottom flask, purged with nitrogen three times, and stirred overnight at room temperature under nitrogen protection. The solution was filtered through Celite and washed twice with dichloromethane. The organic phases below were collected and concentrated under reduced pressure to obtain 3.7 g of Intermediate 5 as a yellow solid (with a yield of 100%).
[0257] Step 3:
##STR00026##
[0258] Intermediate 5 (3.7 g, 4.0 mmol), Intermediate 6 (2.1 g, 6.0 mmol), 2-ethoxyethanol (50 mL) and DMF (50 mL) were sequentially added into a dry 250 mL round-bottom flask and heated to react for 96 h at 100° C. 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 13 as a yellow solid (2.1 g with a yield of 45%). The product structure was confirmed as the target product with a molecular weight of 1075.5.
Synthesis Example 3: Synthesis of Metal Complex 1490
[0259] Step 1:
##STR00027##
[0260] Intermediate 5 (2.7 g, 2.8 mmol), Intermediate 7 (1.5 g, 4.3 mmol), 50 mL of 2-ethoxyethanol and 50 mL of N,N-dimethylformamide were sequentially added to a dry 250 mL round-bottom flask, purged with nitrogen three times, and heated at 100° C. for 96 h under nitrogen protection. The reaction was cooled, filtered through Celite, and washed twice with methanol and n-hexane respectively. Yellow solids on the Celite were dissolved in dichloromethane. The organic phases were collected, concentrated under reduced pressure, and purified through column chromatography to obtain Metal Complex 133 as a yellow solid (1.7 g with a yield of 56.4%). The product was confirmed as the target product with a molecular weight of 1076.5.
Synthesis Example 4: Synthesis of Metal Complex 1496
[0261] Step 1:
##STR00028##
[0262] 2-(3-(t-butyl)-5-fluorophenyl)-4,5-bis(methyl-d3)pyridine (3.4 g, 12.9 mmol), iridium trichloride trihydrate (1.8 g, 5.1 mmol), 45 mL of 2-ethoxyethanol and 15 mL of water were sequentially added to a dry 250 mL round-bottom flask, purged with nitrogen three times, and heated and stirred for 24 h at 130° C. under nitrogen protection. The solution was cooled, filtered, washed three times with methanol and n-hexane respectively, and suction-filtrated to dryness to obtain 3.1 g of Intermediate 8 (with a yield of 81%).
[0263] Step 2:
##STR00029##
[0264] Intermediate 8 (3.1 g, 2.1 mmol), 100 mL of anhydrous dichloromethane, 10 mL of methanol and silver trifluoromethanesulfonate (1.2 g, 4.7 mmol) were sequentially added to a dry 250 mL round-bottom flask, purged with nitrogen three times, and stirred overnight at room temperature under nitrogen protection. The solution was filtered through Celite and washed twice with dichloromethane. The organic phases below were collected and concentrated under reduced pressure to obtain 3.7 g of Intermediate 9 as a yellow solid (with a yield of 95%).
[0265] Step 3:
##STR00030##
[0266] Intermediate 9 (2.0 g, 2.1 mmol), Intermediate 3 (0.9 g, 3.3 mmol), 2-ethoxyethanol (40 mL) and DMAc (40 mL) were sequentially added into a dry 250 mL round-bottom flask and heated to react for 96 h at 100° C. under N.sub.2 protection. The reaction was cooled, filtered, and washed twice with methanol, n-hexane and dichloromethane separately to obtain Metal Complex 1496 as a yellow solid (0.5 g with a yield of 24%). The product structure was confirmed as the target product with a molecular weight of 987.4.
[0267] 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
Device Example 1
[0268] 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 241 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 A1 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 Example 2
[0269] The implementation mode in Device Example 2 was the same as that in Device Example 1, except that in the EML, Metal Complex 241 of the present disclosure was replaced with Metal Complex 1490.
Device Comparative Example 1
[0270] The implementation mode in Device Comparative Example 1 was the same as that in Device Example 1, except that in the EML, Metal Complex 241 of the present disclosure was replaced with Compound GD1.
[0271] 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 Device Example 1, Device Example 2 and Device Comparative Example 1 Device ID HIL HTL EBL EML HBL ETL Example 1 Compound Compound Compound Compound Compound Compound ET:Liq HI HT H1 H1:Compound HB (40:60) (350 Å) (100 Å) (350 Å) (50 Å) H2:Metal Complex (50 Å) 241 (47:47:6) (400 Å) Example 2 Compound Compound Compound Compound Compound Compound ET:Liq HI HT H1 H1:Compound HB (40:60) (350 Å) (100 Å) (350 Å) (50 Å) H2:Metal Complex (50 Å) 1490 (47:47:6) (400 Å) Comparative Compound Compound Compound Compound Compound Compound ET:Liq Example 1 HI HT H1 H1:Compound HB (40:60) (350 Å) (100 Å) (350 Å) (50 Å) H2:GD1 (47:47:6) (50 Å) (400 Å)
[0272] The structures of the materials used in the devices are shown as follows:
##STR00031## ##STR00032## ##STR00033##
[0273] Current-voltage-luminance (IVL) characteristics of the devices were measured. CIE data, maximum emission wavelengths λ.sub.max, full widths at half maximum (FWHMs) and current efficiency (CE) of the devices were measured at 1000 cd/m.sup.2; external quantum efficiency (EQE) data was tested at a constant current of 15 mA/cm.sup.2; and 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 Device data in Device Example 1, Device Example 2 and Device Comparative Example 1 FWHM CE Device ID CIE (x, y) λ.sub.max (nm) (nm) (cd/A) EQE (%) LT 97(h) Example 1 (0.339, 0.635) 529 45.7 91 23.35 25 Example 2 (0.474, 0.521) 561 77.1 86 23.28 80.4 Comparative (0.354, 0.624) 531 52.2 87 22.83 1.8 Example 1
[0274] From the data shown in Table 2, compared to those in Device Comparative Example 1, the CE and EQE in Device Example 1 are improved by 4.6% and 2.3%, respectively, and the lifetime in Device Example 1 reaches 25 h, which is unexpectedly and significantly improved by 13.9 times compared to the lifetime (1.8 h) in Device Comparative Example 1 In addition, compared to those in Device Comparative Example 1, the λ.sub.max in Device Example 1 is blue-shifted by 2 nm, and the FWHM in Device Example 1 is narrowed by 6.5 nm, providing more saturated green light. Compared to Device Comparative Example 1, Device Example 1 has higher efficiency and an excellent lifetime, exhibits more saturated green light and has significantly improved overall performance of the device, indicating that the metal complex of the present disclosure has a substituent R.sub.A at a particular substitution position in a ligand L.sub.a and has an excellent effect of improving the device performance compared to the metal complex having a substituent not represented by Formula 2 at the particular substitution position in the ligand L.sub.a.
[0275] On the basis of Example 1, the metal complex in Example 2 further has substitutions in the ligands L.sub.a and L.sub.b. On the basis that Device Example 1 has excellent device performance, the maximum emission wavelength in Device Example 2 can be adjusted to obtain a device emitting yellow light, and the device lifetime in Device Example 2 is improved by about 3.22 times. At present, in a white light OLED lamp for daily use, white light is mainly generated through a cooperation of a yellow light light-emitting unit and a blue light light-emitting unit. The metal complex of the present disclosure can show excellent device performance through a further modification of substituents and has broad prospects in commercial applications of yellow light or white light.
Device Comparative Example 2
[0276] The implementation mode in Device Comparative Example 2 was the same as that in Device Example 1, except that in the EML, Metal Complex 241 of the present disclosure was replaced with Compound GD2.
[0277] Detailed structures and thicknesses of layers of the device 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 structure in Device Comparative Example 2 Device ID HIL HTL EBL EML HBL ETL Comparative Compound Compound Compound Compound Compound Compound ET:Liq Example 2 HI HT H1 H1:Compound HB (40:60) (350 Å) (100 Å) (350 Å) (50 Å) H2:GD2 (47:47:6) (50 Å) (400 Å)
[0278] The structure of the new material used in the device is shown as follows:
##STR00034##
[0279] IVL characteristics of the device were measured. CIE data, a maximum emission wavelength λ.sub.max and an FWHM of the device were measured at 1000 cd/m.sup.2; and EQE data was tested at a constant current of 15 mA/cm.sup.2. The data was recorded and shown in Table 4.
TABLE-US-00004 TABLE 4 Device data in Device Comparative Example 2 FWHM Device ID CIE (x, y) λ.sub.max (nm) (nm) EQE (%) Example 1 (0.339, 0.635) 529 45.7 23.35 Comparative (0.343, 0.633) 528 50.8 21.05 Example 2
[0280] From the data shown in Table 4, compared to those in Device Comparative Example 2, the FWHM in Device Example 1 is narrowed by 5.1 nm, and the EQE in Device Example 1 is improved by 10.9%. Device Example 1 has higher efficiency, more saturated green light and significantly improved overall performance of the device, indicating that the metal complex of the present disclosure has a substituent R.sub.A at a particular substitution position in a ligand L.sub.a and has an excellent effect of improving the device performance compared to the metal complex having a substituent represented by Formula 2 at a non-particular substitution position in the ligand L.sub.a.
Device Example 3
[0281] The implementation mode in Device Example 3 was the same as that in Device Example 1, except that in the EML, Metal Complex 241 of the present disclosure was replaced with Metal Complex 13 of the present disclosure, and in the EML, a ratio of Compound H1, Compound H2 and Metal Complex 13 was 63:31:6.
Device Comparative Example 3
[0282] The implementation in Device Comparative Example 3 was the same as that in Device Example 3, except that in the EML, Metal Complex 13 of the present disclosure was replaced with Compound GD3.
[0283] 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 Device Example 3 and Device Comparative Example 3 Device ID HIL HTL EBL EML HBL ETL Example 3 Compound Compound Compound Compound Compound Compound ET:Liq HI HT H1 H1:Compound HB (40:60) (350 Å) (100 Å) (350 Å) (50 Å) H2:Metal Complex (50 Å) 13 (63:31:6) (400 Å) Comparative Compound Compound Compound Compound Compound Compound ET:Liq Example 3 HI HT H1 H1:Compound HB (40:60) (350 Å) (100 Å) (350 Å) (50 Å) H2:GD3 (63:31:6) (50 Å) (400 Å)
[0284] The structures of the new materials used in the devices are shown as follows:
##STR00035##
[0285] IVL characteristics of the devices were measured. CIE data, maximum emission wavelengths λ.sub.max, FWHMs and CE of the devices were measured at 1000 cd/m.sup.2; EQE data was tested at a constant current of 15 mA/cm.sup.2; and lifetime (LT97) data was tested at a constant current of 80 mA/cm.sup.2. The data was recorded and shown in Table 6.
TABLE-US-00006 TABLE 6 Device data in Device Example 3 and Device Comparative Example 3 FWHM CE Device ID CIE (x, y) λ.sub.max (nm) (nm) (cd/A) EQE (%) LT 97(h) Example 3 (0.367, 0.616) 535 43.3 107 24.52 47.3 Comparative (0.345, 0.633) 532 36.8 106 23.89 31.7 Example 3
[0286] From the data shown in Table 6, compared to that in Device Comparative Example 3, the CE in Device Example 3 is slightly improved, and although the FWHM in Device Example 3 is 6.5 nm wider than that in Device Comparative Example 3, the FWHM (43.3 nm) in Device Example 3 is already at a relatively high level. Most importantly, compared to the already very excellent EQE and lifetime in Comparative Example 3, the EQE and lifetime in Example 3 are improved by 2.6% and 49.2%, respectively, which is very rare and commendable. Compared to Device Comparative Example 3, Device Example 3 has higher efficiency and an excellent lifetime, indicating that the metal complex of the present disclosure has a substituent R.sub.A at a particular substitution position in a ligand L.sub.a and can significantly improve overall performance of the device compared to the metal complex not having a substituent represented by Formula 2 at the particular substitution position in the ligand L.sub.a.
[0287] The above results show that the metal complex disclosed in the present disclosure comprises the ligand L.sub.a having the structure of Formula 1A (having the substituent represented by Formula 2 at the particular substitution position) and the ligand L.sub.b having the structure of Formula 1B (having a particular substituent at the particular substitution position), and in the case where the device efficiency can be maintained at a high level in the art, compared to the metal complex having the substituent not represented by Formula 2 at the particular substitution position in the ligand L.sub.a and the metal complex having the substituent represented by Formula 2 at the non-particular substitution position in the ligand L.sub.a, the metal complex disclosed in the present disclosure can further improve the luminescence performance, efficiency or lifetime of the device, exhibit more saturated luminescence and significantly improve the overall performance of the device. The metal complex disclosed in the present disclosure has huge advantages and broad prospects in industrial applications.
[0288] 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 from specific embodiments and preferred embodiments described herein. Many of materials and structures described herein may be substituted with other materials and structures without departing from the spirit of the present disclosure. It is to be understood that various theories as to why the present disclosure works are not intended to be limitative.