ORGANIC ELECTROLUMINESCENT MATERIAL AND DEVICE THEREOF
20220372055 · 2022-11-24
Assignee
Inventors
- Zhen Wang (Beijing, CN)
- Hongbo Li (Beijing, CN)
- Ming Sang (Beijing, CN)
- Wei Cai (Beijing, CN)
- Chi Yuen Raymond Kwong (Beijing, CN)
- Chuanjun Xia (Beijing, CN)
Cpc classification
H10K85/6574
ELECTRICITY
H10K85/626
ELECTRICITY
H10K85/6572
ELECTRICITY
H10K85/615
ELECTRICITY
H10K85/6576
ELECTRICITY
International classification
Abstract
Provided are an organic electroluminescent material and a device thereof. The organic electroluminescent material is a metal complex including a ligand L.sub.a having a structure of Formula 1, and the metal complex can be used as luminescent materials in electroluminescent devices. These new compounds, when used in electroluminescent devices, can show better performance, provide lower device voltage and higher device efficiency, and significantly improve the comprehensive performance of devices. Further provided are an electroluminescent device including the metal complex and a compound composition including the metal complex.
Claims
1. A metal complex, comprising a metal M and a ligand L.sub.a coordinated with the metal M, wherein the metal M is selected from metals having a relative atomic mass greater than 40, and L.sub.a has a structure represented by Formula 1: ##STR00080## wherein in Formula 1, Cy is, at each occurrence identically or differently, selected from a substituted or unsubstituted aromatic ring having 6 to 24 ring atoms, a substituted or unsubstituted heteroaromatic ring having 5 to 24 ring atoms or combinations thereof; X is selected from the group consisting of O, S, Se, NR′, CR′R′, SiR′R′, and GeR′R′; when two R′ are present, the two R′ are identical or different; X.sub.1 to X.sub.7 are, at each occurrence identically or differently, selected from C, CR.sub.x or N; at least one of X.sub.1 to X.sub.4 is C and is attached to Cy; X.sub.1, X.sub.2, X.sub.3 or X.sub.4 is attached to the metal M through a metal-carbon bond or a metal-nitrogen bond; at least one of X.sub.1 to X.sub.7 is CR.sub.x, wherein the R.sub.x is cyano or fluorine; A has a structure represented by Formula 2: ##STR00081## wherein a is selected from 1, 2, 3, 4 or 5; A.sub.1 is, at each occurrence identically or differently, selected from the group consisting of: O, S, Se, NR″, SiR″R″, GeR″R″, BR″, PR″, P(O)R″, following groups unsubstituted or substituted by one or at least two R.sub.a1: alkylene having 1 to 20 carbon atoms, heteroalkylene having 1 to 20 carbon atoms, cycloalkylene having 3 to 20 carbon atoms, heterocyclene having 3 to 20 ring atoms, phenylene and heteroarylene having 5 to 6 ring atoms, and combinations thereof; A.sub.2 is, at each occurrence identically or differently, selected from the group consisting of: O, S, Se, NR″, SiR″R″, GeR″R″, BR″, PR″, P(O)R″, following groups unsubstituted or substituted by one or at least two R.sub.a2: alkylene having 1 to 20 carbon atoms, heteroalkylene having 1 to 20 carbon atoms, cycloalkylene having 3 to 20 carbon atoms, heterocyclene having 3 to 20 ring atoms, arylene having 6 to 30 carbon atoms and heteroarylene having 3 to 30 carbon atoms, and combinations thereof; R′, R″, R.sub.x, 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 aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof; adjacent substituents R′, R″, R.sub.x, R.sub.a2, R.sub.a3 can be optionally joined to form a ring; the length of A is at least 6.7 Å; “” represents a position where A is attached; when A.sub.1 is selected from phenylene unsubstituted or substituted by one or at least two R.sub.a1 or heteroarylene having 5 to 6 ring atoms unsubstituted or substituted by one or at least two R.sub.a1, A.sub.2 and R.sub.a1 need to satisfy the following conditions: 1) A.sub.2 that is directly attached to A.sub.1 is, at each occurrence identically or differently, selected from the group consisting of: O, S, Se, NR″, SiR″R″, GeR″R″, BR″, PR″, P(O)R″, following groups unsubstituted or substituted by one or at least two R.sub.a2: alkylene having 1 to 20 carbon atoms, heteroalkylene having 1 to 20 carbon atoms, cycloalkylene having 3 to 20 carbon atoms and heterocyclene having 3 to 20 ring atoms, and combinations thereof; and 2) R.sub.a1 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 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.
2. The metal complex of claim 1, wherein A.sub.1 is, at each occurrence identically or differently, selected from phenylene unsubstituted or substituted by one or at least two R.sub.a1 or heteroarylene having 5 to 6 ring atoms unsubstituted or substituted by one or at least two R.sub.a1; A.sub.2 is, at each occurrence identically or differently, selected from the group consisting of: O, S, NR″, SiR″R″, GeR″R″, following groups unsubstituted or substituted by one or at least two R.sub.a2: alkylene having 1 to 6 carbon atoms, cycloalkylene having 3 to 20 ring carbon atoms and heterocyclene having 3 to 20 ring atoms, and combinations thereof; preferably, A.sub.1 is, at each occurrence identically or differently, selected from phenylene unsubstituted or substituted by one or at least two R.sub.a1 or heteroarylene having 6 ring atoms unsubstituted or substituted by one or at least two R.sub.a1; A.sub.2 is, at each occurrence identically or differently, selected from cycloalkylene having 3 to 20 ring carbon atoms unsubstituted or substituted by one or at least two R.sub.a2, heterocyclene having 3 to 20 ring atoms unsubstituted or substituted by one or at least two R.sub.a2 or combinations thereof; more preferably, A.sub.1 is, at each occurrence identically or differently, selected from phenylene unsubstituted or substituted by one or at least two R.sub.a1; A.sub.2 is, at each occurrence identically or differently, selected from cycloalkylene having 5 to 12 ring carbon atoms unsubstituted or substituted by one or at least two R.sub.a2, heterocyclene unsubstituted or substituted by one or at least two R.sub.a2 and having 5 to 12 ring atoms or combinations thereof.
3. The metal complex of claim 1, wherein A.sub.1 is, at each occurrence identically or differently, selected from the group consisting of: O, S, NR″, SiR″R″, GeR″R″, following groups unsubstituted or substituted by one or at least two R.sub.a1: alkylene having 1 to 20 carbon atoms, heteroalkylene having 1 to 20 carbon atoms, cycloalkylene having 3 to 20 carbon atoms and heterocyclene having 3 to 20 ring atoms, and combinations thereof; A.sub.2 is, at each occurrence identically or differently, selected from following groups unsubstituted or substituted by one or at least two R.sub.a2: alkylene having 1 to 20 carbon atoms, heteroalkylene having 1 to 20 carbon atoms, cycloalkylene having 3 to 20 carbon atoms, heterocyclene having 3 to 20 ring atoms, arylene having 6 to 30 carbon atoms, heteroarylene having 3 to 30 carbon atoms, and combinations thereof; preferably, A.sub.1 is, at each occurrence identically or differently, selected from the group consisting of: O, S, NR″, SiR″R″, GeR″R″, following groups unsubstituted or substituted by one or at least two R.sub.a1: cycloalkylene having 3 to 10 carbon atoms and heterocyclene having 3 to 10 ring atoms, and combinations thereof; A.sub.2 is, at each occurrence identically or differently, selected from following groups unsubstituted or substituted by one or at least two R.sub.a2: cycloalkylene having 3 to 10 carbon atoms, heterocyclene having 3 to 10 ring atoms, arylene having 6 to 18 carbon atoms and heteroarylene having 3 to 18 ring atoms, and combinations thereof.
4. The metal complex of claim 1, wherein Cy is selected from any one of the group consisting of the following structures: ##STR00082## wherein, R represents, at each occurrence identically or differently, mono-substitution, multiple substitutions or no substitution; when a plurality of R are present in any one of those structures, the plurality of R are identical 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; two adjacent substituents R can be optionally joined to form a ring; “#” represents a position where the metal M is attached, and ##STR00083## represents a position where X.sub.1, X.sub.2, X.sub.3 or X.sub.4 is attached.
5. The metal complex of claim 1, wherein the metal complex has a general formula of M(L.sub.a).sub.m(L.sub.b).sub.n(L.sub.c).sub.q; wherein, M is, at each occurrence identically or differently, selected from the group consisting of Cu, Ag, Au, Ru, Rh, Pd, Os, Ir, and Pt; preferably, M is, at each occurrence identically or differently, selected from Pt or Ir; L.sub.a, L.sub.b, and L.sub.c are a first ligand, a second ligand and a third ligand coordinated to the metal M, respectively, and L.sub.c is identical to or different from L.sub.a or L.sub.b; wherein L.sub.a, L.sub.b, and L.sub.c can be optionally joined to form a multidentate ligand; m is selected from 1, 2 or 3, n is selected from 0, 1 or 2, q is selected from 0, 1 or 2, and m+n+q equals an oxidation state of the metal M; when m is greater than or equal to 2, a plurality of L.sub.a are identical or different; when n is equal to 2, two L.sub.b are identical or different; when q is equal to 2, two L.sub.c are identical or different; L.sub.a is, at each occurrence identically or differently, selected from the group consisting of: ##STR00084## ##STR00085## ##STR00086## ##STR00087## ##STR00088## ##STR00089## X is selected from the group consisting of O, S, Se, NR′, CR′R′, SiR′R′, and GeR′R′; when two R′ are present, the two R′ are identical or different; R and R.sub.x represent, at each occurrence identically or differently, mono-substitution, multiple substitutions or no substitution; at least one of R.sub.x is fluorine or cyano; A has a structure represented by Formula 2: ##STR00090## wherein a is selected from 1, 2, 3, 4 or 5; A.sub.1 is, at each occurrence identically or differently, selected from the group consisting of: O, S, Se, NR″, SiR″R″, GeR″R″, BR″, PR″, P(O)R″, following groups unsubstituted or substituted by one or at least two R.sub.a1: alkylene having 1 to 20 carbon atoms, heteroalkylene having 1 to 20 carbon atoms, cycloalkylene having 3 to 20 carbon atoms, heterocyclene having 3 to 20 ring atoms, phenylene and heteroarylene having 5 to 6 ring atoms, and combinations thereof; A.sub.2 is, at each occurrence identically or differently, selected from the group consisting of: O, S, Se, NR″, SiR″R″, GeR″R″, BR″, PR″, P(O)R″, following groups unsubstituted or substituted by one or at least two R.sub.a2: alkylene having 1 to 20 carbon atoms, heteroalkylene having 1 to 20 carbon atoms, cycloalkylene having 3 to 20 carbon atoms, heterocyclene having 3 to 20 ring atoms, arylene having 6 to 30 carbon atoms and heteroarylene having 3 to 30 carbon atoms, and combinations thereof; R, R′, R″, R.sub.x, 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 aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof; adjacent substituents R, R′, R″, R.sub.x, R.sub.a2, R.sub.a3 can be optionally joined to form a ring; the length of A is at least 6.7 Å; “” represents a position where A is attached; when A.sub.1 is selected from phenylene unsubstituted or substituted by one or at least two R.sub.a1 or heteroarylene having 5 to 6 ring atoms unsubstituted or substituted by one or at least two R.sub.a1, A.sub.2 and R.sub.a1 need to satisfy the following conditions: 1) A.sub.2 that is directly attached to A.sub.1 is, at each occurrence identically or differently, selected from the group consisting of: O, S, Se, NR″, SiR″R″, GeR″R″, BR″, PR″, P(O)R″, alkylene having 1 to 20 carbon atoms unsubstituted or substituted by one or at least two R.sub.a2, heteroalkylene having 1 to 20 carbon atoms unsubstituted or substituted by one or at least two R.sub.a2, cycloalkylene having 3 to 20 carbon atoms unsubstituted or substituted by one or at least two R.sub.a2, heterocyclene having 3 to 20 ring atoms unsubstituted or substituted by one or at least two R.sub.a2, and combinations thereof; and 2) R.sub.a1 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 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; L.sub.b and L.sub.c are, at each occurrence identically or differently, selected from the group consisting of the following structures: ##STR00091## wherein, R.sub.a and R.sub.b represent, at each occurrence identically or differently, mono-substitution, multiple substitutions or no substitution; X.sub.b is, at each occurrence identically or differently, selected from the group consisting of: O, S, Se, NR.sub.N1, and CR.sub.C1R.sub.C2; R.sub.a, 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; 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.
6. The metal complex of claim 1, wherein the metal complex is Ir(L.sub.a).sub.m(L.sub.b).sub.3-m and has a structure represented by Formula 3: ##STR00092## wherein, m is selected from 1, 2 or 3; when m is selected from 1, two L.sub.b are identical or different; when m is selected from 2 or 3, a plurality of L.sub.a are identical or different; Y.sub.1 to Y.sub.4 are, at each occurrence identically or differently, selected from CR.sub.y or N; X is selected from the group consisting of O, S, Se, NR′, CR′R′, SiR′R′, and GeR′R′; when two R′ are present, the two R′ are identical or different; X.sub.3 to X.sub.7 are, at each occurrence identically or differently, selected from CR.sub.x or N; at least one of X.sub.3 to X.sub.7 is CR.sub.x, wherein the R.sub.x is a cyano group or fluorine; A has a structure represented by Formula 2: ##STR00093## wherein a is selected from 1, 2, 3, 4 or 5; A.sub.1 is, at each occurrence identically or differently, selected from the group consisting of: O, S, Se, NR″, SiR″R″, GeR″R″, BR″, PR″, P(O)R″, following groups unsubstituted or substituted by one or at least two R.sub.a1: alkylene having 1 to 20 carbon atoms, heteroalkylene having 1 to 20 carbon atoms, cycloalkylene having 3 to 20 carbon atoms, heterocyclene having 3 to 20 ring atoms, phenylene and heteroarylene having 5 to 6 ring atoms, and combinations thereof; A.sub.2 is, at each occurrence identically or differently, selected from the group consisting of: O, S, Se, NR″, SiR″R″, GeR″R″, BR″, PR″, P(O)R″, following groups unsubstituted or substituted by one or at least two R.sub.a2: alkylene having 1 to 20 carbon atoms, heteroalkylene having 1 to 20 carbon atoms, cycloalkylene having 3 to 20 carbon atoms, heterocyclene having 3 to 20 ring atoms, arylene having 6 to 30 carbon atoms and heteroarylene having 3 to 30 carbon atoms, and combinations thereof; R′, R″, R.sub.x, R.sub.y, R.sub.a1, R.sub.a2, R.sub.a3, and R.sub.1 to R.sub.8 are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted 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.1 to R.sub.8 can be optionally joined to form a ring; adjacent substituents R′, R″, R.sub.x, R.sub.y, R.sub.a2, R.sub.a3 can be optionally joined to form a ring; the length of A is at least 6.7 Å; “” represents a position where A is attached; when A.sub.1 is, at each occurrence identically or differently, selected from phenylene unsubstituted or substituted by one or at least two R.sub.a1 or heteroarylene having 5 to 6 ring atoms unsubstituted or substituted by one or at least two R.sub.a1, A.sub.2 and R.sub.a1 need to satisfy the following conditions: 1) A.sub.2 that is directly attached to A.sub.1 is, at each occurrence identically or differently, selected from the group consisting of: O, S, Se, NR″, SiR″R″, GeR″R″, BR″, PR″, P(O)R″, alkylene having 1 to 20 carbon atoms unsubstituted or substituted by one or at least two R.sub.a2, heteroalkylene having 1 to 20 carbon atoms unsubstituted or substituted by one or at least two R.sub.a2, cycloalkylene having 3 to 20 carbon atoms unsubstituted or substituted by one or at least two R.sub.a2, heterocyclene having 3 to 20 ring atoms unsubstituted or substituted by one or at least two R.sub.a2, and combinations thereof; and 2) R.sub.a1 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 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.
7. The metal complex of claim 1, wherein X is selected from O or S, and a is selected from 1, 2 or 3; preferably, a is 1.
8. The metal complex of claim 6, wherein X.sub.3 to X.sub.7 are, at each occurrence identically or differently, selected from CR.sub.x; and/or Y.sub.1 to Y.sub.4 are, at each occurrence identically or differently, selected from CR.sub.Y.
9. The metal complex of claim 6, wherein at least one of X.sub.3 to X.sub.7 is N, and/or at least one of Y.sub.1 to Y.sub.4 is N.
10. The metal complex of claim 6, wherein at least one of X.sub.3 to X.sub.7 is CR.sub.x, wherein the R.sub.x is cyano or fluorine; remaining R.sub.x 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, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, a cyano group, and combinations thereof; preferably, at least one of X.sub.5 to X.sub.7 is CR.sub.x, wherein the R.sub.x is cyano or fluorine; remaining R.sub.x are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, fluorine, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms, substituted or unsubstituted aryl having 6 to 12 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 12 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 6 carbon atoms, a cyano group, and combinations thereof; more preferably, X.sub.7 is CR.sub.x, wherein the R.sub.x is cyano or fluorine; remaining R.sub.x are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms, and combinations thereof.
11. The metal complex of claim 1, wherein R.sub.a1 is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 4 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, a hydroxyl group, a sulfanyl group, and combinations thereof; preferably, R.sub.a1 is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, fluorine, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms, substituted or unsubstituted alkylsilyl having 4 to 15 carbon atoms, and combinations thereof; more preferably, R.sub.a1 is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, fluorine, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, cyclopentyl, cyclohexyl, deuterated methyl, deuterated ethyl, deuterated propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated t-butyl, deuterated cyclopentyl, deuterated cyclohexyl, trimethylsilyl, and combinations thereof.
12. The metal complex of claim 1, wherein 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 arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, a hydroxyl group, a sulfanyl group, and combinations thereof; preferably, R.sub.a2 and R.sub.a3 are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, fluorine, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms, substituted or unsubstituted aryl having 6 to 18 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 18 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 15 carbon atoms, and combinations thereof; more preferably, R.sub.a2 and R.sub.a3 are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, fluorine, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, cyclopentyl, cyclohexyl, deuterated methyl, deuterated ethyl, deuterated propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated t-butyl, deuterated cyclopentyl, deuterated cyclohexyl, phenyl, pyridyl, trimethylsilyl, and combinations thereof.
13. The metal complex of claim 1, wherein A is, at each occurrence identically or differently, selected from the group consisting of: ##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## and combinations thereof; optionally, hydrogen in the above groups can be partially or fully substituted with deuterium; wherein “” represents a position where A is attached.
14. The metal complex of claim 6, wherein R.sub.y is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, and combinations thereof; preferably, at least one R.sub.y is selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, and combinations thereof.
15. The metal complex of claim 6, wherein at least one or at least two of R.sub.5 to R.sub.8 is(are), at each occurrence identically or differently, selected from substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms or combinations thereof, and the total number of carbon atoms in all R.sub.5 to R.sub.8 is at least 4.
16. The metal complex of claim 6, wherein at least one or at least two or at least three or all of R.sub.2, R.sub.3, R.sub.6, and R.sub.7 is(are) selected from the group consisting of: deuterium, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, and combinations thereof; preferably, at least one or at least two or at least three or all of R.sub.2, R.sub.3, R.sub.6, and R.sub.7 is(are) selected from the group consisting of: deuterium, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, and combinations thereof; more preferably, at least one or at least two or at least three or all of R.sub.2, R.sub.3, R.sub.6, and R.sub.7 is(are) selected from the group consisting of: deuterium, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, cyclopentyl, cyclohexyl, neopentyl, t-pentyl, and combinations thereof; optionally, hydrogen in the above groups can be partially or fully substituted with deuterium.
17. The metal complex of claim 5, wherein L.sub.a is, at each occurrence identically or differently, selected from the group consisting of: ##STR00124## ##STR00125## ##STR00126## ##STR00127## ##STR00128## ##STR00129## ##STR00130## ##STR00131## ##STR00132## ##STR00133## ##STR00134## ##STR00135## ##STR00136## ##STR00137## ##STR00138## ##STR00139## ##STR00140## ##STR00141## ##STR00142## ##STR00143## ##STR00144## ##STR00145## ##STR00146## ##STR00147## ##STR00148## ##STR00149## ##STR00150## ##STR00151## ##STR00152## ##STR00153## ##STR00154## ##STR00155## ##STR00156## ##STR00157## ##STR00158## ##STR00159## ##STR00160## ##STR00161## ##STR00162## ##STR00163## ##STR00164## ##STR00165## ##STR00166## ##STR00167## ##STR00168## ##STR00169## ##STR00170## ##STR00171## ##STR00172## ##STR00173## ##STR00174## ##STR00175## ##STR00176## ##STR00177## ##STR00178## ##STR00179## ##STR00180## ##STR00181## ##STR00182## ##STR00183## ##STR00184## ##STR00185## ##STR00186## ##STR00187## ##STR00188## ##STR00189## ##STR00190## ##STR00191## ##STR00192## ##STR00193## ##STR00194## ##STR00195## ##STR00196## ##STR00197## ##STR00198## ##STR00199## ##STR00200## ##STR00201## ##STR00202## ##STR00203## ##STR00204## ##STR00205## ##STR00206## ##STR00207## ##STR00208## ##STR00209## ##STR00210## ##STR00211## ##STR00212## ##STR00213## ##STR00214## ##STR00215## ##STR00216## ##STR00217## ##STR00218## ##STR00219## ##STR00220## ##STR00221## ##STR00222## ##STR00223## ##STR00224## ##STR00225## ##STR00226## ##STR00227## ##STR00228## ##STR00229## ##STR00230## ##STR00231## ##STR00232## ##STR00233## ##STR00234## ##STR00235## ##STR00236## ##STR00237## ##STR00238## ##STR00239## ##STR00240## ##STR00241## ##STR00242## ##STR00243## ##STR00244## ##STR00245## ##STR00246## ##STR00247## ##STR00248## ##STR00249## ##STR00250## ##STR00251## ##STR00252## ##STR00253## ##STR00254## ##STR00255## ##STR00256## ##STR00257## ##STR00258## ##STR00259## ##STR00260## ##STR00261## ##STR00262## ##STR00263## ##STR00264## ##STR00265## ##STR00266## ##STR00267## ##STR00268## ##STR00269## ##STR00270## ##STR00271## ##STR00272## ##STR00273## ##STR00274## ##STR00275## ##STR00276## ##STR00277## ##STR00278## ##STR00279## ##STR00280## ##STR00281## ##STR00282## ##STR00283## ##STR00284## ##STR00285## ##STR00286## ##STR00287## ##STR00288## ##STR00289## ##STR00290## ##STR00291## ##STR00292## ##STR00293## ##STR00294## ##STR00295## ##STR00296## ##STR00297## ##STR00298## ##STR00299## ##STR00300## ##STR00301## ##STR00302## ##STR00303## ##STR00304## ##STR00305## ##STR00306## ##STR00307## ##STR00308## ##STR00309## ##STR00310## ##STR00311## ##STR00312## ##STR00313## ##STR00314## ##STR00315## ##STR00316## ##STR00317## ##STR00318## ##STR00319## ##STR00320## ##STR00321## ##STR00322## ##STR00323## ##STR00324## ##STR00325## ##STR00326## ##STR00327## ##STR00328## ##STR00329## ##STR00330## ##STR00331## ##STR00332## ##STR00333## ##STR00334## ##STR00335## ##STR00336## ##STR00337## ##STR00338## ##STR00339## ##STR00340## ##STR00341## ##STR00342##
18. The metal complex of claim 17, wherein L.sub.b is, at each occurrence identically or differently, selected from the group consisting of: ##STR00343## ##STR00344## ##STR00345## ##STR00346## ##STR00347## ##STR00348## ##STR00349## ##STR00350## ##STR00351## ##STR00352## ##STR00353## ##STR00354## ##STR00355## ##STR00356## ##STR00357## ##STR00358## ##STR00359## ##STR00360## ##STR00361## ##STR00362## ##STR00363## ##STR00364## ##STR00365## ##STR00366## ##STR00367## ##STR00368## ##STR00369## ##STR00370## ##STR00371## ##STR00372## ##STR00373## ##STR00374## ##STR00375## ##STR00376## ##STR00377## ##STR00378## ##STR00379## ##STR00380## ##STR00381## ##STR00382## ##STR00383## ##STR00384## ##STR00385## ##STR00386## ##STR00387## ##STR00388## ##STR00389## ##STR00390## ##STR00391## ##STR00392## ##STR00393## ##STR00394## ##STR00395## ##STR00396## ##STR00397## ##STR00398## ##STR00399## ##STR00400## ##STR00401## ##STR00402## ##STR00403## ##STR00404## ##STR00405## ##STR00406## ##STR00407## ##STR00408## ##STR00409## ##STR00410## ##STR00411## ##STR00412## ##STR00413## ##STR00414## ##STR00415## ##STR00416##
19. The metal complex of claim 18, wherein L.sub.c is, at each occurrence identically or differently, selected from the group consisting of: ##STR00417## ##STR00418## ##STR00419## ##STR00420## ##STR00421## ##STR00422## ##STR00423## ##STR00424## ##STR00425## ##STR00426## ##STR00427## ##STR00428## ##STR00429## ##STR00430## ##STR00431## ##STR00432## ##STR00433## ##STR00434## ##STR00435## ##STR00436## ##STR00437## ##STR00438## ##STR00439## ##STR00440## ##STR00441## ##STR00442## ##STR00443## ##STR00444## ##STR00445## ##STR00446## ##STR00447## ##STR00448## ##STR00449## ##STR00450## ##STR00451## ##STR00452## ##STR00453## ##STR00454## ##STR00455## ##STR00456## ##STR00457## ##STR00458## ##STR00459## ##STR00460## ##STR00461## ##STR00462## ##STR00463## ##STR00464## ##STR00465## ##STR00466## ##STR00467## ##STR00468##
20. The metal complex of claim 19, wherein the metal complex has a structure of Ir(L.sub.a).sub.2(L.sub.b) or Ir(L.sub.a)(L.sub.b).sub.2 or Ir(L.sub.a).sub.3, wherein L.sub.a is, at each occurrence identically or differently, selected from any one or any two or any three of the group consisting of L.sub.a1 to L.sub.a938, and L.sub.b is selected from any one or any two of the group consisting of L.sub.b1 to L.sub.b328; or the metal complex has a structure of Ir(L.sub.a).sub.2(L.sub.c) or Ir(L.sub.a)(L.sub.c).sub.2, wherein L.sub.a is, at each occurrence identically or differently, selected from any one or any two of the group consisting of L.sub.a1 to L.sub.a938, and L.sub.c is selected from any one or any two of the group consisting of L.sub.c1 to L.sub.c360; or the metal complex has a structure of Ir(L.sub.a)(L.sub.b)(L.sub.c), wherein L.sub.a is, at each occurrence identically or differently, selected from any one of the group consisting of L.sub.a1 to L.sub.a938, L.sub.b is selected from any one of the group consisting of L.sub.b1 to L.sub.b328, and L.sub.c is selected from any one of the group consisting of L.sub.c1 to L.sub.c360; preferably, the metal complex is selected from the group consisting of metal complex 1 to metal complex 1900, 1901 and 1902, wherein metal complex 1 to metal complex 1900, 1901 and 1902 have a structure of IrL.sub.a(L.sub.b).sub.2, wherein two L.sub.b are identical, and L.sub.a and L.sub.b correspond to structures in the following table, respectively: TABLE-US-00008 Metal Metal complex L.sub.a L.sub.b complex L.sub.a L.sub.b 1 L.sub.a5 L.sub.b1 2 L.sub.a5 L.sub.b3 3 L.sub.a5 L.sub.b4 4 L.sub.a5 L.sub.b8 5 L.sub.a5 L.sub.b10 6 L.sub.a5 L.sub.b12 7 L.sub.a5 L.sub.b13 8 L.sub.a5 L.sub.b17 9 L.sub.a5 L.sub.b21 10 L.sub.a5 L.sub.b22 11 L.sub.a5 L.sub.b26 12 L.sub.a5 L.sub.b28 13 L.sub.a5 L.sub.b30 14 L.sub.a5 L.sub.b31 15 L.sub.a5 L.sub.b35 16 L.sub.a5 L.sub.b37 17 L.sub.a5 L.sub.b38 18 L.sub.a5 L.sub.b39 19 L.sub.a5 L.sub.b40 20 L.sub.a5 L.sub.b41 21 L.sub.a5 L.sub.b42 22 L.sub.a5 L.sub.b43 23 L.sub.a5 L.sub.b44 24 L.sub.a5 L.sub.b45 25 L.sub.a5 L.sub.b71 26 L.sub.a5 L.sub.b72 27 L.sub.a5 L.sub.b79 28 L.sub.a5 L.sub.b80 29 L.sub.a5 L.sub.b81 30 L.sub.a5 L.sub.b99 31 L.sub.a5 L.sub.b112 32 L.sub.a5 L.sub.b151 33 L.sub.a5 L.sub.b153 34 L.sub.a5 L.sub.b164 35 L.sub.a5 L.sub.b166 36 L.sub.a5 L.sub.b209 37 L.sub.a5 L.sub.b287 38 L.sub.a5 L.sub.b299 39 L.sub.a13 L.sub.b1 40 L.sub.a13 L.sub.b3 41 L.sub.a13 L.sub.b4 42 L.sub.a13 L.sub.b8 43 L.sub.a13 L.sub.b10 44 L.sub.a13 L.sub.b12 45 L.sub.a13 L.sub.b13 46 L.sub.a13 L.sub.b17 47 L.sub.a13 L.sub.b21 48 L.sub.a13 L.sub.b22 49 L.sub.a13 L.sub.b26 50 L.sub.a13 L.sub.b28 51 L.sub.a13 L.sub.b30 52 L.sub.a13 L.sub.b31 53 L.sub.a13 L.sub.b35 54 L.sub.a13 L.sub.b37 55 L.sub.a13 L.sub.b38 56 L.sub.a13 L.sub.b39 57 L.sub.a13 L.sub.b40 58 L.sub.a13 L.sub.b41 59 L.sub.a13 L.sub.b42 60 L.sub.a13 L.sub.b43 61 L.sub.a13 L.sub.b44 62 L.sub.a13 L.sub.b45 63 L.sub.a13 L.sub.b71 64 L.sub.a13 L.sub.b72 65 L.sub.a13 L.sub.b79 66 L.sub.a13 L.sub.b80 67 L.sub.a13 L.sub.b81 68 L.sub.a13 L.sub.b99 69 L.sub.a13 L.sub.b112 70 L.sub.a13 L.sub.b151 71 L.sub.a13 L.sub.b153 72 L.sub.a13 L.sub.b164 73 L.sub.a13 L.sub.b166 74 L.sub.a13 L.sub.b209 75 L.sub.a13 L.sub.b287 76 L.sub.a13 L.sub.b299 77 L.sub.a14 L.sub.b1 78 L.sub.a14 L.sub.b3 79 L.sub.a14 L.sub.b4 80 L.sub.a14 L.sub.b8 81 L.sub.a14 L.sub.b10 82 L.sub.a14 L.sub.b12 83 L.sub.a14 L.sub.b13 84 L.sub.a14 L.sub.b17 85 L.sub.a14 L.sub.b21 86 L.sub.a14 L.sub.b22 87 L.sub.a14 L.sub.b26 88 L.sub.a14 L.sub.b28 89 L.sub.a14 L.sub.b30 90 L.sub.a14 L.sub.b31 91 L.sub.a14 L.sub.b35 92 L.sub.a14 L.sub.b37 93 L.sub.a14 L.sub.b38 94 L.sub.a14 L.sub.b39 95 L.sub.a14 L.sub.b40 96 L.sub.a14 L.sub.b41 97 L.sub.a14 L.sub.b42 98 L.sub.a14 L.sub.b43 99 L.sub.a14 L.sub.b44 100 L.sub.a14 L.sub.b45 101 L.sub.a14 L.sub.b71 102 L.sub.a14 L.sub.b72 103 L.sub.a14 L.sub.b79 104 L.sub.a14 L.sub.b80 105 L.sub.a14 L.sub.b81 106 L.sub.a14 L.sub.b99 107 L.sub.a14 L.sub.b112 108 L.sub.a14 L.sub.b151 109 L.sub.a14 L.sub.b153 110 L.sub.a14 L.sub.b164 111 L.sub.a14 L.sub.b166 112 L.sub.a14 L.sub.b209 113 L.sub.a14 L.sub.b287 114 L.sub.a14 L.sub.b299 115 L.sub.a18 L.sub.b1 116 L.sub.a18 L.sub.b3 117 L.sub.a18 L.sub.b4 118 L.sub.a18 L.sub.b8 119 L.sub.a18 L.sub.b10 120 L.sub.a18 L.sub.b12 121 L.sub.a18 L.sub.b13 122 L.sub.a18 L.sub.b17 123 L.sub.a18 L.sub.b21 124 L.sub.a18 L.sub.b22 125 L.sub.a18 L.sub.b26 126 L.sub.a18 L.sub.b28 127 L.sub.a18 L.sub.b30 128 L.sub.a18 L.sub.b31 129 L.sub.a18 L.sub.b35 130 L.sub.a18 L.sub.b37 131 L.sub.a18 L.sub.b38 132 L.sub.a18 L.sub.b39 133 L.sub.a18 L.sub.b40 134 L.sub.a18 L.sub.b41 135 L.sub.a18 L.sub.b42 136 L.sub.a18 L.sub.b43 137 L.sub.a18 L.sub.b44 138 L.sub.a18 L.sub.b45 139 L.sub.a18 L.sub.b71 140 L.sub.a18 L.sub.b72 141 L.sub.a18 L.sub.b79 142 L.sub.a18 L.sub.b80 143 L.sub.a18 L.sub.b81 144 L.sub.a18 L.sub.b99 145 L.sub.a18 L.sub.b112 146 L.sub.a18 L.sub.b151 147 L.sub.a18 L.sub.b153 148 L.sub.a18 L.sub.b164 149 L.sub.a18 L.sub.b166 150 L.sub.a18 L.sub.b209 151 L.sub.a18 L.sub.b287 152 L.sub.a18 L.sub.b299 153 L.sub.a20 L.sub.b1 154 L.sub.a20 L.sub.b3 155 L.sub.a20 L.sub.b4 156 L.sub.a20 L.sub.b8 157 L.sub.a20 L.sub.b10 158 L.sub.a20 L.sub.b12 159 L.sub.a20 L.sub.b13 160 L.sub.a20 L.sub.b17 161 L.sub.a20 L.sub.b21 162 L.sub.a20 L.sub.b22 163 L.sub.a20 L.sub.b26 164 L.sub.a20 L.sub.b28 165 L.sub.a20 L.sub.b30 166 L.sub.a20 L.sub.b31 167 L.sub.a20 L.sub.b35 168 L.sub.a20 L.sub.b37 169 L.sub.a20 L.sub.b38 170 L.sub.a20 L.sub.b39 171 L.sub.a20 L.sub.b40 172 L.sub.a20 L.sub.b41 173 L.sub.a20 L.sub.b42 174 L.sub.a20 L.sub.b43 175 L.sub.a20 L.sub.b44 176 L.sub.a20 L.sub.b45 177 L.sub.a20 L.sub.b71 178 L.sub.a20 L.sub.b72 179 L.sub.a20 L.sub.b79 180 L.sub.a20 L.sub.b80 181 L.sub.a20 L.sub.b81 182 L.sub.a20 L.sub.b99 183 L.sub.a20 L.sub.b112 184 L.sub.a20 L.sub.b151 185 L.sub.a20 L.sub.b153 186 L.sub.a20 L.sub.b164 187 L.sub.a20 L.sub.b166 188 L.sub.a20 L.sub.b209 189 L.sub.a20 L.sub.b287 190 L.sub.a20 L.sub.b299 191 L.sub.a57 L.sub.b1 192 L.sub.a57 L.sub.b3 193 L.sub.a57 L.sub.b4 194 L.sub.a57 L.sub.b8 195 L.sub.a57 L.sub.b10 196 L.sub.a57 L.sub.b12 197 L.sub.a57 L.sub.b13 198 L.sub.a57 L.sub.b17 199 L.sub.a57 L.sub.b21 200 L.sub.a57 L.sub.b22 201 L.sub.a57 L.sub.b26 202 L.sub.a57 L.sub.b28 203 L.sub.a57 L.sub.b30 204 L.sub.a57 L.sub.b31 205 L.sub.a57 L.sub.b35 206 L.sub.a57 L.sub.b37 207 L.sub.a57 L.sub.b38 208 L.sub.a57 L.sub.b39 209 L.sub.a57 L.sub.b40 210 L.sub.a57 L.sub.b41 211 L.sub.a57 L.sub.b42 212 L.sub.a57 L.sub.b43 213 L.sub.a57 L.sub.b44 214 L.sub.a57 L.sub.b45 215 L.sub.a57 L.sub.b71 216 L.sub.a57 L.sub.b72 217 L.sub.a57 L.sub.b79 218 L.sub.a57 L.sub.b80 219 L.sub.a57 L.sub.b81 220 L.sub.a57 L.sub.b99 221 L.sub.a57 L.sub.b112 222 L.sub.a57 L.sub.b151 223 L.sub.a57 L.sub.b153 224 L.sub.a57 L.sub.b164 225 L.sub.a57 L.sub.b166 226 L.sub.a57 L.sub.b209 227 L.sub.a57 L.sub.b287 228 L.sub.a57 L.sub.b299 229 L.sub.a70 L.sub.b1 230 L.sub.a70 L.sub.b3 231 L.sub.a70 L.sub.b4 232 L.sub.a70 L.sub.b8 233 L.sub.a70 L.sub.b10 234 L.sub.a70 L.sub.b12 235 L.sub.a70 L.sub.b13 236 L.sub.a70 L.sub.b17 237 L.sub.a70 L.sub.b21 238 L.sub.a70 L.sub.b22 239 L.sub.a70 L.sub.b26 240 L.sub.a70 L.sub.b28 241 L.sub.a70 L.sub.b30 242 L.sub.a70 L.sub.b31 243 L.sub.a70 L.sub.b35 244 L.sub.a70 L.sub.b37 245 L.sub.a70 L.sub.b38 246 L.sub.a70 L.sub.b39 247 L.sub.a70 L.sub.b40 248 L.sub.a70 L.sub.b41 249 L.sub.a70 L.sub.b42 250 L.sub.a70 L.sub.b43 251 L.sub.a70 L.sub.b44 252 L.sub.a70 L.sub.b45 253 L.sub.a70 L.sub.b71 254 L.sub.a70 L.sub.b72 255 L.sub.a70 L.sub.b79 256 L.sub.a70 L.sub.b80 257 L.sub.a70 L.sub.b81 258 L.sub.a70 L.sub.b99 259 L.sub.a70 L.sub.b112 260 L.sub.a70 L.sub.b151 261 L.sub.a70 L.sub.b153 262 L.sub.a70 L.sub.b164 263 L.sub.a70 L.sub.b166 264 L.sub.a70 L.sub.b209 265 L.sub.a70 L.sub.b287 266 L.sub.a70 L.sub.b299 267 L.sub.a79 L.sub.b1 268 L.sub.a79 L.sub.b3 269 L.sub.a79 L.sub.b4 270 L.sub.a79 L.sub.b8 271 L.sub.a79 L.sub.b10 272 L.sub.a79 L.sub.b12 273 L.sub.a79 L.sub.b13 274 L.sub.a79 L.sub.b17 275 L.sub.a79 L.sub.b21 276 L.sub.a79 L.sub.b22 277 L.sub.a79 L.sub.b26 278 L.sub.a79 L.sub.b28 279 L.sub.a79 L.sub.b30 280 L.sub.a79 L.sub.b31 281 L.sub.a79 L.sub.b35 282 L.sub.a79 L.sub.b37 283 L.sub.a79 L.sub.b38 284 L.sub.a79 L.sub.b39 285 L.sub.a79 L.sub.b40 286 L.sub.a79 L.sub.b41 287 L.sub.a79 L.sub.b42 288 L.sub.a79 L.sub.b43 289 L.sub.a79 L.sub.b44 290 L.sub.a79 L.sub.b45 291 L.sub.a79 L.sub.b71 292 L.sub.a79 L.sub.b72 293 L.sub.a79 L.sub.b79 294 L.sub.a79 L.sub.b80 295 L.sub.a79 L.sub.b81 296 L.sub.a79 L.sub.b99 297 L.sub.a79 L.sub.b112 298 L.sub.a79 L.sub.b151 299 L.sub.a79 L.sub.b153 300 L.sub.a79 L.sub.b164 301 L.sub.a79 L.sub.b166 302 L.sub.a79 L.sub.b209 303 L.sub.a79 L.sub.b287 304 L.sub.a79 L.sub.b299 305 L.sub.a92 L.sub.b1 306 L.sub.a92 L.sub.b3 307 L.sub.a92 L.sub.b4 308 L.sub.a92 L.sub.b8 309 L.sub.a92 L.sub.b10 310 L.sub.a92 L.sub.b12 311 L.sub.a92 L.sub.b13 312 L.sub.a92 L.sub.b17 313 L.sub.a92 L.sub.b21 314 L.sub.a92 L.sub.b22 315 L.sub.a92 L.sub.b26 316 L.sub.a92 L.sub.b28 317 L.sub.a92 L.sub.b30 318 L.sub.a92 L.sub.b31 319 L.sub.a92 L.sub.b35 320 L.sub.a92 L.sub.b37 321 L.sub.a92 L.sub.b38 322 L.sub.a92 L.sub.b39 323 L.sub.a92 L.sub.b40 324 L.sub.a92 L.sub.b41 325 L.sub.a92 L.sub.b42 326 L.sub.a92 L.sub.b43 327 L.sub.a92 L.sub.b44 328 L.sub.a92 L.sub.b45 329 L.sub.a92 L.sub.b71 330 L.sub.a92 L.sub.b72 331 L.sub.a92 L.sub.b79 332 L.sub.a92 L.sub.b80 333 L.sub.a92 L.sub.b81 334 L.sub.a92 L.sub.b99 335 L.sub.a92 L.sub.b112 336 L.sub.a92 L.sub.b151 337 L.sub.a92 L.sub.b153 338 L.sub.a92 L.sub.b164 339 L.sub.a92 L.sub.b166 340 L.sub.a92 L.sub.b209 341 L.sub.a92 L.sub.b287 342 L.sub.a92 L.sub.b299 343 L.sub.a113 L.sub.b1 344 L.sub.a113 L.sub.b3 345 L.sub.a113 L.sub.b4 346 L.sub.a113 L.sub.b8 347 L.sub.a113 L.sub.b10 348 L.sub.a113 L.sub.b12 349 L.sub.a113 L.sub.b13 350 L.sub.a113 L.sub.b17 351 L.sub.a113 L.sub.b21 352 L.sub.a113 L.sub.b22 353 L.sub.a113 L.sub.b26 354 L.sub.a113 L.sub.b28 355 L.sub.a113 L.sub.b30 356 L.sub.a113 L.sub.b31 357 L.sub.a113 L.sub.b35 358 L.sub.a113 L.sub.b37 359 L.sub.a113 L.sub.b38 360 L.sub.a113 L.sub.b39 361 L.sub.a113 L.sub.b40 362 L.sub.a113 L.sub.b41 363 L.sub.a113 L.sub.b42 364 L.sub.a113 L.sub.b43 365 L.sub.a113 L.sub.b44 366 L.sub.a113 L.sub.b45 367 L.sub.a113 L.sub.b71 368 L.sub.a113 L.sub.b72 369 L.sub.a113 L.sub.b79 370 L.sub.a113 L.sub.b80 371 L.sub.a113 L.sub.b81 372 L.sub.a113 L.sub.b99 373 L.sub.a113 L.sub.b112 374 L.sub.a113 L.sub.b151 375 L.sub.a113 L.sub.b153 376 L.sub.a113 L.sub.b164 377 L.sub.a113 L.sub.b166 378 L.sub.a113 L.sub.b209 379 L.sub.a113 L.sub.b287 380 L.sub.a113 L.sub.b299 381 L.sub.a231 L.sub.b1 382 L.sub.a231 L.sub.b3 383 L.sub.a231 L.sub.b4 384 L.sub.a231 L.sub.b8 385 L.sub.a231 L.sub.b10 386 L.sub.a231 L.sub.b12 387 L.sub.a231 L.sub.b13 388 L.sub.a231 L.sub.b17 389 L.sub.a231 L.sub.b21 390 L.sub.a231 L.sub.b22 391 L.sub.a231 L.sub.b26 392 L.sub.a231 L.sub.b28 393 L.sub.a231 L.sub.b30 394 L.sub.a231 L.sub.b31 395 L.sub.a231 L.sub.b35 396 L.sub.a231 L.sub.b37 397 L.sub.a231 L.sub.b38 398 L.sub.a231 L.sub.b39 399 L.sub.a231 L.sub.b40 400 L.sub.a231 L.sub.b41 401 L.sub.a231 L.sub.b42 402 L.sub.a231 L.sub.b43 403 L.sub.a231 L.sub.b44 404 L.sub.a231 L.sub.b45 405 L.sub.a231 L.sub.b71 406 L.sub.a231 L.sub.b72 407 L.sub.a231 L.sub.b79 408 L.sub.a231 L.sub.b80 409 L.sub.a231 L.sub.b81 410 L.sub.a231 L.sub.b99 411 L.sub.a231 L.sub.b112 412 L.sub.a231 L.sub.b151 413 L.sub.a231 L.sub.b153 414 L.sub.a231 L.sub.b164 415 L.sub.a231 L.sub.b166 416 L.sub.a231 L.sub.b209 417 L.sub.a231 L.sub.b287 418 L.sub.a231 L.sub.b299 419 L.sub.a236 L.sub.b1 420 L.sub.a236 L.sub.b3 421 L.sub.a236 L.sub.b4 422 L.sub.a236 L.sub.b8 423 L.sub.a236 L.sub.b10 424 L.sub.a236 L.sub.b12 425 L.sub.a236 L.sub.b13 426 L.sub.a236 L.sub.b17 427 L.sub.a236 L.sub.b21 428 L.sub.a236 L.sub.b22 429 L.sub.a236 L.sub.b26 430 L.sub.a236 L.sub.b28 431 L.sub.a236 L.sub.b30 432 L.sub.a236 L.sub.b31 433 L.sub.a236 L.sub.b35 434 L.sub.a236 L.sub.b37 435 L.sub.a236 L.sub.b38 436 L.sub.a236 L.sub.b39 437 L.sub.a236 L.sub.b40 438 L.sub.a236 L.sub.b41 439 L.sub.a236 L.sub.b42 440 L.sub.a236 L.sub.b43 441 L.sub.a236 L.sub.b44 442 L.sub.a236 L.sub.b45 443 L.sub.a236 L.sub.b71 444 L.sub.a236 L.sub.b72 445 L.sub.a236 L.sub.b79 446 L.sub.a236 L.sub.b80 447 L.sub.a236 L.sub.b81 448 L.sub.a236 L.sub.b99 449 L.sub.a236 L.sub.b112 450 L.sub.a236 L.sub.b151 451 L.sub.a236 L.sub.b153 452 L.sub.a236 L.sub.b164 453 L.sub.a236 L.sub.b166 454 L.sub.a236 L.sub.b209 455 L.sub.a236 L.sub.b287 456 L.sub.a236 L.sub.b299 457 L.sub.a237 L.sub.b1 458 L.sub.a237 L.sub.b3 459 L.sub.a237 L.sub.b4 460 L.sub.a237 L.sub.b8 461 L.sub.a237 L.sub.b10 462 L.sub.a237 L.sub.b12 463 L.sub.a237 L.sub.b13 464 L.sub.a237 L.sub.b17 465 L.sub.a237 L.sub.b21 466 L.sub.a237 L.sub.b22 467 L.sub.a237 L.sub.b26 468 L.sub.a237 L.sub.b28 469 L.sub.a237 L.sub.b30 470 L.sub.a237 L.sub.b31 471 L.sub.a237 L.sub.b35 472 L.sub.a237 L.sub.b37 473 L.sub.a237 L.sub.b38 474 L.sub.a237 L.sub.b39 475 L.sub.a237 L.sub.b40 476 L.sub.a237 L.sub.b41 477 L.sub.a237 L.sub.b42 478 L.sub.a237 L.sub.b43 479 L.sub.a237 L.sub.b44 480 L.sub.a237 L.sub.b45 481 L.sub.a237 L.sub.b71 482 L.sub.a237 L.sub.b72 483 L.sub.a237 L.sub.b79 484 L.sub.a237 L.sub.b80 485 L.sub.a237 L.sub.b81 486 L.sub.a237 L.sub.b99 487 L.sub.a237 L.sub.b112 488 L.sub.a237 L.sub.b151 489 L.sub.a237 L.sub.b153 490 L.sub.a237 L.sub.b164 491 L.sub.a237 L.sub.b166 492 L.sub.a237 L.sub.b209 493 L.sub.a237 L.sub.b287 494 L.sub.a237 L.sub.b299 495 L.sub.a238 L.sub.b1 496 L.sub.a238 L.sub.b3 497 L.sub.a238 L.sub.b4 498 L.sub.a238 L.sub.b8 499 L.sub.a238 L.sub.b10 500 L.sub.a238 L.sub.b12 501 L.sub.a238 L.sub.b13 502 L.sub.a238 L.sub.b17 503 L.sub.a238 L.sub.b21 504 L.sub.a238 L.sub.b22 505 L.sub.a238 L.sub.b26 506 L.sub.a238 L.sub.b28 507 L.sub.a238 L.sub.b30 508 L.sub.a238 L.sub.b31 509 L.sub.a238 L.sub.b35 510 L.sub.a238 L.sub.b37 511 L.sub.a238 L.sub.b38 512 L.sub.a238 L.sub.b39 513 L.sub.a238 L.sub.b40 514 L.sub.a238 L.sub.b41 515 L.sub.a238 L.sub.b42 516 L.sub.a238 L.sub.b43 517 L.sub.a238 L.sub.b44 518 L.sub.a238 L.sub.b45 519 L.sub.a238 L.sub.b71 520 L.sub.a238 L.sub.b72 521 L.sub.a238 L.sub.b79 522 L.sub.a238 L.sub.b80 523 L.sub.a238 L.sub.b81 524 L.sub.a238 L.sub.b99 525 L.sub.a238 L.sub.b112 526 L.sub.a238 L.sub.b151 527 L.sub.a238 L.sub.b153 528 L.sub.a238 L.sub.b164 529 L.sub.a238 L.sub.b166 530 L.sub.a238 L.sub.b209 531 L.sub.a238 L.sub.b287 532 L.sub.a238 L.sub.b299 533 L.sub.a239 L.sub.b1 534 L.sub.a239 L.sub.b3 535 L.sub.a239 L.sub.b4 536 L.sub.a239 L.sub.b8 537 L.sub.a239 L.sub.b10 538 L.sub.a239 L.sub.b12 539 L.sub.a239 L.sub.b13 540 L.sub.a239 L.sub.b17 541 L.sub.a239 L.sub.b21 542 L.sub.a239 L.sub.b22 543 L.sub.a239 L.sub.b26 544 L.sub.a239 L.sub.b28 545 L.sub.a239 L.sub.b30 546 L.sub.a239 L.sub.b31 547 L.sub.a239 L.sub.b35 548 L.sub.a239 L.sub.b37 549 L.sub.a239 L.sub.b38 550 L.sub.a239 L.sub.b39 551 L.sub.a239 L.sub.b40 552 L.sub.a239 L.sub.b41 553 L.sub.a239 L.sub.b42 554 L.sub.a239 L.sub.b43 555 L.sub.a239 L.sub.b44 556 L.sub.a239 L.sub.b45 557 L.sub.a239 L.sub.b71 558 L.sub.a239 L.sub.b72 559 L.sub.a239 L.sub.b79 560 L.sub.a239 L.sub.b80 561 L.sub.a239 L.sub.b81 562 L.sub.a239 L.sub.b99 563 L.sub.a239 L.sub.b112 564 L.sub.a239 L.sub.b151 565 L.sub.a239 L.sub.b153 566 L.sub.a239 L.sub.b164 567 L.sub.a239 L.sub.b166 568 L.sub.a239 L.sub.b209 569 L.sub.a239 L.sub.b287 570 L.sub.a239 L.sub.b299 571 L.sub.a245 L.sub.b1 572 L.sub.a245 L.sub.b3 573 L.sub.a245 L.sub.b4 574 L.sub.a245 L.sub.b8 575 L.sub.a245 L.sub.b10 576 L.sub.a245 L.sub.b12 577 L.sub.a245 L.sub.b13 578 L.sub.a245 L.sub.b17 579 L.sub.a245 L.sub.b21 580 L.sub.a245 L.sub.b22 581 L.sub.a245 L.sub.b26 582 L.sub.a245 L.sub.b28 583 L.sub.a245 L.sub.b30 584 L.sub.a245 L.sub.b31 585 L.sub.a245 L.sub.b35 586 L.sub.a245 L.sub.b37 587 L.sub.a245 L.sub.b38 588 L.sub.a245 L.sub.b39 589 L.sub.a245 L.sub.b40 590 L.sub.a245 L.sub.b41 591 L.sub.a245 L.sub.b42 592 L.sub.a245 L.sub.b43 593 L.sub.a245 L.sub.b44 594 L.sub.a245 L.sub.b45 595 L.sub.a245 L.sub.b71 596 L.sub.a245 L.sub.b72 597 L.sub.a245 L.sub.b79 598 L.sub.a245 L.sub.b80 599 L.sub.a245 L.sub.b81 600 L.sub.a245 L.sub.b99 601 L.sub.a245 L.sub.b112 602 L.sub.a245 L.sub.b151 603 L.sub.a245 L.sub.b153 604 L.sub.a245 L.sub.b164 605 L.sub.a245 L.sub.b166 606 L.sub.a245 L.sub.b209 607 L.sub.a245 L.sub.b287 608 L.sub.a245 L.sub.b299 609 L.sub.a250 L.sub.b1 610 L.sub.a250 L.sub.b3 611 L.sub.a250 L.sub.b4 612 L.sub.a250 L.sub.b8 613 L.sub.a250 L.sub.b10 614 L.sub.a250 L.sub.b12 615 L.sub.a250 L.sub.b13 616 L.sub.a250 L.sub.b17 617 L.sub.a250 L.sub.b21 618 L.sub.a250 L.sub.b22 619 L.sub.a250 L.sub.b26 620 L.sub.a250 L.sub.b28 621 L.sub.a250 L.sub.b30 622 L.sub.a250 L.sub.b31 623 L.sub.a250 L.sub.b35 624 L.sub.a250 L.sub.b37 625 L.sub.a250 L.sub.b38 626 L.sub.a250 L.sub.b39 627 L.sub.a250 L.sub.b40 628 L.sub.a250 L.sub.b41 629 L.sub.a250 L.sub.b42 630 L.sub.a250 L.sub.b43 631 L.sub.a250 L.sub.b44 632 L.sub.a250 L.sub.b45 633 L.sub.a250 L.sub.b71 634 L.sub.a250 L.sub.b72 635 L.sub.a250 L.sub.b79 636 L.sub.a250 L.sub.b80 637 L.sub.a250 L.sub.b81 638 L.sub.a250 L.sub.b99 639 L.sub.a250 L.sub.b112 640 L.sub.a250 L.sub.b151 641 L.sub.a250 L.sub.b153 642 L.sub.a250 L.sub.b164 643 L.sub.a250 L.sub.b166 644 L.sub.a250 L.sub.b209 645 L.sub.a250 L.sub.b287 646 L.sub.a250 L.sub.b299 647 L.sub.a251 L.sub.b1 648 L.sub.a251 L.sub.b3 649 L.sub.a251 L.sub.b4 650 L.sub.a251 L.sub.b8 651 L.sub.a251 L.sub.b10 652 L.sub.a251 L.sub.b12 653 L.sub.a251 L.sub.b13 654 L.sub.a251 L.sub.b17 655 L.sub.a251 L.sub.b21 656 L.sub.a251 L.sub.b22 657 L.sub.a251 L.sub.b26 658 L.sub.a251 L.sub.b28 659 L.sub.a251 L.sub.b30 660 L.sub.a251 L.sub.b31 661 L.sub.a251 L.sub.b35 662 L.sub.a251 L.sub.b37 663 L.sub.a251 L.sub.b38 664 L.sub.a251 L.sub.b39 665 L.sub.a251 L.sub.b40 666 L.sub.a251 L.sub.b41 667 L.sub.a251 L.sub.b42 668 L.sub.a251 L.sub.b43 669 L.sub.a251 L.sub.b44 670 L.sub.a251 L.sub.b45 671 L.sub.a251 L.sub.b71 672 L.sub.a251 L.sub.b72 673 L.sub.a251 L.sub.b79 674 L.sub.a251 L.sub.b80 675 L.sub.a251 L.sub.b81 676 L.sub.a251 L.sub.b99 677 L.sub.a251 L.sub.b112 678 L.sub.a251 L.sub.b151 679 L.sub.a251 L.sub.b153 680 L.sub.a251 L.sub.b164 681 L.sub.a251 L.sub.b166 682 L.sub.a251 L.sub.b209 683 L.sub.a251 L.sub.b287 684 L.sub.a251 L.sub.b299 685 L.sub.a252 L.sub.b1 686 L.sub.a252 L.sub.b3 687 L.sub.a252 L.sub.b4 688 L.sub.a252 L.sub.b8 689 L.sub.a252 L.sub.b10 690 L.sub.a252 L.sub.b12 691 L.sub.a252 L.sub.b13 692 L.sub.a252 L.sub.b17 693 L.sub.a252 L.sub.b21 694 L.sub.a252 L.sub.b22 695 L.sub.a252 L.sub.b26 696 L.sub.a252 L.sub.b28 697 L.sub.a252 L.sub.b30 698 L.sub.a252 L.sub.b31 699 L.sub.a252 L.sub.b35 700 L.sub.a252 L.sub.b37 701 L.sub.a252 L.sub.b38 702 L.sub.a252 L.sub.b39 703 L.sub.a252 L.sub.b40 704 L.sub.a252 L.sub.b41 705 L.sub.a252 L.sub.b42 706 L.sub.a252 L.sub.b43 707 L.sub.a252 L.sub.b44 708 L.sub.a252 L.sub.b45 709 L.sub.a252 L.sub.b71 710 L.sub.a252 L.sub.b72 711 L.sub.a252 L.sub.b79 712 L.sub.a252 L.sub.b80 713 L.sub.a252 L.sub.b81 714 L.sub.a252 L.sub.b99 715 L.sub.a252 L.sub.b112 716 L.sub.a252 L.sub.b151 717 L.sub.a252 L.sub.b153 718 L.sub.a252 L.sub.b164 719 L.sub.a252 L.sub.b166 720 L.sub.a252 L.sub.b209 721 L.sub.a252 L.sub.b287 722 L.sub.a252 L.sub.b299 723 L.sub.a253 L.sub.b1 724 L.sub.a253 L.sub.b3 725 L.sub.a253 L.sub.b4 726 L.sub.a253 L.sub.b8 727 L.sub.a253 L.sub.b10 728 L.sub.a253 L.sub.b12 729 L.sub.a253 L.sub.b13 730 L.sub.a253 L.sub.b17 731 L.sub.a253 L.sub.b21 732 L.sub.a253 L.sub.b22 733 L.sub.a253 L.sub.b26 734 L.sub.a253 L.sub.b28 735 L.sub.a253 L.sub.b30 736 L.sub.a253 L.sub.b31 737 L.sub.a253 L.sub.b35 738 L.sub.a253 L.sub.b37 739 L.sub.a253 L.sub.b38 740 L.sub.a253 L.sub.b39 741 L.sub.a253 L.sub.b40 742 L.sub.a253 L.sub.b41 743 L.sub.a253 L.sub.b42 744 L.sub.a253 L.sub.b43 745 L.sub.a253 L.sub.b44 746 L.sub.a253 L.sub.b45 747 L.sub.a253 L.sub.b71 748 L.sub.a253 L.sub.b72 749 L.sub.a253 L.sub.b79 750 L.sub.a253 L.sub.b80 751 L.sub.a253 L.sub.b81 752 L.sub.a253 L.sub.b99 753 L.sub.a253 L.sub.b112 754 L.sub.a253 L.sub.b151 755 L.sub.a253 L.sub.b153 756 L.sub.a253 L.sub.b164 757 L.sub.a253 L.sub.b166 758 L.sub.a253 L.sub.b209 759 L.sub.a253 L.sub.b287 760 L.sub.a253 L.sub.b299 761 L.sub.a259 L.sub.b1 762 L.sub.a259 L.sub.b3 763 L.sub.a259 L.sub.b4 764 L.sub.a259 L.sub.b8 765 L.sub.a259 L.sub.b10 766 L.sub.a259 L.sub.b12 767 L.sub.a259 L.sub.b13 768 L.sub.a259 L.sub.b17 769 L.sub.a259 L.sub.b21 770 L.sub.a259 L.sub.b22 771 L.sub.a259 L.sub.b26 772 L.sub.a259 L.sub.b28 773 L.sub.a259 L.sub.b30 774 L.sub.a259 L.sub.b31 775 L.sub.a259 L.sub.b35 776 L.sub.a259 L.sub.b37 777 L.sub.a259 L.sub.b38 778 L.sub.a259 L.sub.b39 779 L.sub.a259 L.sub.b40 780 L.sub.a259 L.sub.b41 781 L.sub.a259 L.sub.b42 782 L.sub.a259 L.sub.b43 783 L.sub.a259 L.sub.b44 784 L.sub.a259 L.sub.b45 785 L.sub.a259 L.sub.b71 786 L.sub.a259 L.sub.b72 787 L.sub.a259 L.sub.b79 788 L.sub.a259 L.sub.b80 789 L.sub.a259 L.sub.b81 790 L.sub.a259 L.sub.b99 791 L.sub.a259 L.sub.b112 792 L.sub.a259 L.sub.b151 793 L.sub.a259 L.sub.b53 794 L.sub.a259 L.sub.b164 795 L.sub.a259 L.sub.b166 796 L.sub.a259 L.sub.b209 797 L.sub.a259 L.sub.b287 798 L.sub.a259 L.sub.b299 799 L.sub.a264 L.sub.b1 800 L.sub.a264 L.sub.b3 801 L.sub.a264 L.sub.b4 802 L.sub.a264 L.sub.b8 803 L.sub.a264 L.sub.b10 804 L.sub.a264 L.sub.b12 805 L.sub.a264 L.sub.b13 806 L.sub.a264 L.sub.b17 807 L.sub.a264 L.sub.b21 808 L.sub.a264 L.sub.b22 809 L.sub.a264 L.sub.b26 810 L.sub.a264 L.sub.b28 811 L.sub.a264 L.sub.b30 812 L.sub.a264 L.sub.b31 813 L.sub.a264 L.sub.b35 814 L.sub.a264 L.sub.b37 815 L.sub.a264 L.sub.b38 816 L.sub.a264 L.sub.b39 817 L.sub.a264 L.sub.b40 818 L.sub.a264 L.sub.b41 819 L.sub.a264 L.sub.b42 820 L.sub.a264 L.sub.b43 821 L.sub.a264 L.sub.b44 822 L.sub.a264 L.sub.b45 823 L.sub.a264 L.sub.b71 824 L.sub.a264 L.sub.b72 825 L.sub.a264 L.sub.b79 826 L.sub.a264 L.sub.b80 827 L.sub.a264 L.sub.b81 828 L.sub.a264 L.sub.b99 829 L.sub.a264 L.sub.b112 830 L.sub.a264 L.sub.b151 831 L.sub.a264 L.sub.b153 832 L.sub.a264 L.sub.b164 833 L.sub.a264 L.sub.b166 834 L.sub.a264 L.sub.b209 835 L.sub.a264 L.sub.b287 836 L.sub.a264 L.sub.b299 837 L.sub.a269 L.sub.b1 838 L.sub.a269 L.sub.b3 839 L.sub.a269 L.sub.b4 840 L.sub.a269 L.sub.b8 841 L.sub.a269 L.sub.b10 842 L.sub.a269 L.sub.b12 843 L.sub.a269 L.sub.b13 844 L.sub.a269 L.sub.b17 845 L.sub.a269 L.sub.b21 846 L.sub.a269 L.sub.b22 847 L.sub.a269 L.sub.b26 848 L.sub.a269 L.sub.b28 849 L.sub.a269 L.sub.b30 850 L.sub.a269 L.sub.b31 851 L.sub.a269 L.sub.b35 852 L.sub.a269 L.sub.b37 853 L.sub.a269 L.sub.b38 854 L.sub.a269 L.sub.b39 855 L.sub.a269 L.sub.b40 856 L.sub.a269 L.sub.b41 857 L.sub.a269 L.sub.b42 858 L.sub.a269 L.sub.b43 859 L.sub.a269 L.sub.b44 860 L.sub.a269 L.sub.b45 861 L.sub.a269 L.sub.b71 862 L.sub.a269 L.sub.b72 863 L.sub.a269 L.sub.b79 864 L.sub.a269 L.sub.b80 865 L.sub.a269 L.sub.b81 866 L.sub.a269 L.sub.b99 867 L.sub.a269 L.sub.b112 868 L.sub.a269 L.sub.b151 869 L.sub.a269 L.sub.b153 870 L.sub.a269 L.sub.b164 871 L.sub.a269 L.sub.b166 872 L.sub.a269 L.sub.b209 873 L.sub.a269 L.sub.b287 874 L.sub.a269 L.sub.b299 875 L.sub.a274 L.sub.b1 876 L.sub.a274 L.sub.b3 877 L.sub.a274 L.sub.b4 878 L.sub.a274 L.sub.b8 879 L.sub.a274 L.sub.b10 880 L.sub.a274 L.sub.b12 881 L.sub.a274 L.sub.b13 882 L.sub.a274 L.sub.b17 883 L.sub.a274 L.sub.b21 884 L.sub.a274 L.sub.b22 885 L.sub.a274 L.sub.b26 886 L.sub.a274 L.sub.b28 887 L.sub.a274 L.sub.b30 888 L.sub.a274 L.sub.b31 889 L.sub.a274 L.sub.b35 890 L.sub.a274 L.sub.b37 891 L.sub.a274 L.sub.b38 892 L.sub.a274 L.sub.b39 893 L.sub.a274 L.sub.b40 894 L.sub.a274 L.sub.b41 895 L.sub.a274 L.sub.b42 896 L.sub.a274 L.sub.b43 897 L.sub.a274 L.sub.b44 898 L.sub.a274 L.sub.b45 899 L.sub.a274 L.sub.b71 900 L.sub.a274 L.sub.b72 901 L.sub.a274 L.sub.b79 902 L.sub.a274 L.sub.b80 903 L.sub.a274 L.sub.b81 904 L.sub.a274 L.sub.b99 905 L.sub.a274 L.sub.b112 906 L.sub.a274 L.sub.b151 907 L.sub.a274 L.sub.b153 908 L.sub.a274 L.sub.b164 909 L.sub.a274 L.sub.b166 910 L.sub.a274 L.sub.b209 911 L.sub.a274 L.sub.b287 912 L.sub.a274 L.sub.b299 913 L.sub.a287 L.sub.b1 914 L.sub.a287 L.sub.b3 915 L.sub.a287 L.sub.b4 916 L.sub.a287 L.sub.b8 917 L.sub.a287 L.sub.b10 918 L.sub.a287 L.sub.b12 919 L.sub.a287 L.sub.b13 920 L.sub.a287 L.sub.b17 921 L.sub.a287 L.sub.b21 922 L.sub.a287 L.sub.b22 923 L.sub.a287 L.sub.b26 924 L.sub.a287 L.sub.b28 925 L.sub.a287 L.sub.b30 926 L.sub.a287 L.sub.b31 927 L.sub.a287 L.sub.b35 928 L.sub.a287 L.sub.b37 929 L.sub.a287 L.sub.b38 930 L.sub.a287 L.sub.b39 931 L.sub.a287 L.sub.b40 932 L.sub.a287 L.sub.b41 933 L.sub.a287 L.sub.b42 934 L.sub.a287 L.sub.b43 935 L.sub.a287 L.sub.b44 936 L.sub.a287 L.sub.b45 937 L.sub.a287 L.sub.b71 938 L.sub.a287 L.sub.b72 939 L.sub.a287 L.sub.b79 940 L.sub.a287 L.sub.b80 941 L.sub.a287 L.sub.b81 942 L.sub.a287 L.sub.b99 943 L.sub.a287 L.sub.b112 944 L.sub.a287 L.sub.b151 945 L.sub.a287 L.sub.b153 946 L.sub.a287 L.sub.b164 947 L.sub.a287 L.sub.b166 948 L.sub.a287 L.sub.b209 949 L.sub.a287 L.sub.b287 950 L.sub.a287 L.sub.b299 951 L.sub.a289 L.sub.b1 952 L.sub.a289 L.sub.b3 953 L.sub.a289 L.sub.b4 954 L.sub.a289 L.sub.b8 955 L.sub.a289 L.sub.b10 956 L.sub.a289 L.sub.b12 957 L.sub.a289 L.sub.b13 958 L.sub.a289 L.sub.b17 959 L.sub.a289 L.sub.b21 960 L.sub.a289 L.sub.b22 961 L.sub.a289 L.sub.b26 962 L.sub.a289 L.sub.b28 963 L.sub.a289 L.sub.b30 964 L.sub.a289 L.sub.b31 965 L.sub.a289 L.sub.b35 966 L.sub.a289 L.sub.b37 967 L.sub.a289 L.sub.b38 968 L.sub.a289 L.sub.b39 969 L.sub.a289 L.sub.b40 970 L.sub.a289 L.sub.b41 971 L.sub.a289 L.sub.b42 972 L.sub.a289 L.sub.b43 973 L.sub.a289 L.sub.b44 974 L.sub.a289 L.sub.b45 975 L.sub.a289 L.sub.b71 976 L.sub.a289 L.sub.b72 977 L.sub.a289 L.sub.b79 978 L.sub.a289 L.sub.b80 979 L.sub.a289 L.sub.b81 980 L.sub.a289 L.sub.b99 981 L.sub.a289 L.sub.b112 982 L.sub.a289 L.sub.b151 983 L.sub.a289 L.sub.b153 984 L.sub.a289 L.sub.b164 985 L.sub.a289 L.sub.b166 986 L.sub.a289 L.sub.b209 987 L.sub.a289 L.sub.b287 988 L.sub.a289 L.sub.b299 989 L.sub.a290 L.sub.b1 990 L.sub.a290 L.sub.b3 991 L.sub.a290 L.sub.b4 992 L.sub.a290 L.sub.b8 993 L.sub.a290 L.sub.b10 994 L.sub.a290 L.sub.b12 995 L.sub.a290 L.sub.b13 996 L.sub.a290 L.sub.b17 997 L.sub.a290 L.sub.b21 998 L.sub.a290 L.sub.b22 999 L.sub.a290 L.sub.b26 1000 L.sub.a290 L.sub.b28 1001 L.sub.a290 L.sub.b30 1002 L.sub.a290 L.sub.b31 1003 L.sub.a290 L.sub.b35 1004 L.sub.a290 L.sub.b37 1005 L.sub.a290 L.sub.b38 1006 L.sub.a290 L.sub.b39 1007 L.sub.a290 L.sub.b40 1008 L.sub.a290 L.sub.b41 1009 L.sub.a290 L.sub.b42 1010 L.sub.a290 L.sub.b43 1011 L.sub.a290 L.sub.b44 1012 L.sub.a290 L.sub.b45 1013 L.sub.a290 L.sub.b71 1014 L.sub.a290 L.sub.b72 1015 L.sub.a290 L.sub.b79 1016 L.sub.a290 L.sub.b80 1017 L.sub.a290 L.sub.b81 1018 L.sub.a290 L.sub.b99 1019 L.sub.a290 L.sub.b112 1020 L.sub.a290 L.sub.b151 1021 L.sub.a290 L.sub.b153 1022 L.sub.a290 L.sub.b164 1023 L.sub.a290 L.sub.b166 1024 L.sub.a290 L.sub.b209 1025 L.sub.a290 L.sub.b287 1026 L.sub.a290 L.sub.b299 1027 L.sub.a297 L.sub.b1 1028 L.sub.a297 L.sub.b3 1029 L.sub.a297 L.sub.b4 1030 L.sub.a297 L.sub.b8 1031 L.sub.a297 L.sub.b10 1032 L.sub.a297 L.sub.b12 1033 L.sub.a297 L.sub.b13 1034 L.sub.a297 L.sub.b17 1035 L.sub.a297 L.sub.b21 1036 L.sub.a297 L.sub.b22 1037 L.sub.a297 L.sub.b26 1038 L.sub.a297 L.sub.b28 1039 L.sub.a297 L.sub.b30 1040 L.sub.a297 L.sub.b31 1041 L.sub.a297 L.sub.b35 1042 L.sub.a297 L.sub.b37 1043 L.sub.a297 L.sub.b38 1044 L.sub.a297 L.sub.b39 1045 L.sub.a297 L.sub.b40 1046 L.sub.a297 L.sub.b41 1047 L.sub.a297 L.sub.b42 1048 L.sub.a297 L.sub.b43 1049 L.sub.a297 L.sub.b44 1050 L.sub.a297 L.sub.b45 1051 L.sub.a297 L.sub.b71 1052 L.sub.a297 L.sub.b72 1053 L.sub.a297 L.sub.b79 1054 L.sub.a297 L.sub.b80 1055 L.sub.a297 L.sub.b81 1056 L.sub.a297 L.sub.b99 1057 L.sub.a297 L.sub.b112 1058 L.sub.a297 L.sub.b151 1059 L.sub.a297 L.sub.b153 1060 L.sub.a297 L.sub.b164 1061 L.sub.a297 L.sub.b166 1062 L.sub.a297 L.sub.b209 1063 L.sub.a297 L.sub.b287 1064 L.sub.a297 L.sub.b299 1065 L.sub.a299 L.sub.b1 1066 L.sub.a299 L.sub.b3 1067 L.sub.a299 L.sub.b4 1068 L.sub.a299 L.sub.b8 1069 L.sub.a299 L.sub.b10 1070 L.sub.a299 L.sub.b12 1071 L.sub.a299 L.sub.b13 1072 L.sub.a299 L.sub.b17 1073 L.sub.a299 L.sub.b21 1074 L.sub.a299 L.sub.b22 1075 L.sub.a299 L.sub.b26 1076 L.sub.a299 L.sub.b28 1077 L.sub.a299 L.sub.b30 1078 L.sub.a299 L.sub.b31 1079 L.sub.a299 L.sub.b35 1080 L.sub.a299 L.sub.b37 1081 L.sub.a299 L.sub.b38 1082 L.sub.a299 L.sub.b39 1083 L.sub.a299 L.sub.b40 1084 L.sub.a299 L.sub.b41 1085 L.sub.a299 L.sub.b42 1086 L.sub.a299 L.sub.b43 1087 L.sub.a299 L.sub.b44 1088 L.sub.a299 L.sub.b45 1089 L.sub.a299 L.sub.b71 1090 L.sub.a299 L.sub.b72 1091 L.sub.a299 L.sub.b79 1092 L.sub.a299 L.sub.b80 1093 L.sub.a299 L.sub.b81 1094 L.sub.a299 L.sub.b99 1095 L.sub.a299 L.sub.b112 1096 L.sub.a299 L.sub.b151 1097 L.sub.a299 L.sub.b153 1098 L.sub.a299 L.sub.b164 1099 L.sub.a299 L.sub.b166 1100 L.sub.a299 L.sub.b209 1101 L.sub.a299 L.sub.b287 1102 L.sub.a299 L.sub.b299 1103 L.sub.a307 L.sub.b1 1104 L.sub.a307 L.sub.b3 1105 L.sub.a307 L.sub.b4 1106 L.sub.a307 L.sub.b8 1107 L.sub.a307 L.sub.b10 1108 L.sub.a307 L.sub.b12 1109 L.sub.a307 L.sub.b13 1110 L.sub.a307 L.sub.b17 1111 L.sub.a307 L.sub.b21 1112 L.sub.a307 L.sub.b22 1113 L.sub.a307 L.sub.b26 1114 L.sub.a307 L.sub.b28 1115 L.sub.a307 L.sub.b30 1116 L.sub.a307 L.sub.b31 1117 L.sub.a307 L.sub.b35 1118 L.sub.a307 L.sub.b37 1119 L.sub.a307 L.sub.b38 1120 L.sub.a307 L.sub.b39 1121 L.sub.a307 L.sub.b40 1122 L.sub.a307 L.sub.b41 1123 L.sub.a307 L.sub.b42 1124 L.sub.a307 L.sub.b43 1125 L.sub.a307 L.sub.b44 1126 L.sub.a307 L.sub.b45 1127 L.sub.a307 L.sub.b71 1128 L.sub.a307 L.sub.b72 1129 L.sub.a307 L.sub.b79 1130 L.sub.a307 L.sub.b80 1131 L.sub.a307 L.sub.b81 1132 L.sub.a307 L.sub.b99 1133 L.sub.a307 L.sub.b112 1134 L.sub.a307 L.sub.b151 1135 L.sub.a307 L.sub.b153 1136 L.sub.a307 L.sub.b164 1137 L.sub.a307 L.sub.b166 1138 L.sub.a307 L.sub.b209 1139 L.sub.a307 L.sub.b287 1140 L.sub.a307 L.sub.b299 1141 L.sub.a317 L.sub.b1 1142 L.sub.a317 L.sub.b3 1143 L.sub.a317 L.sub.b4 1144 L.sub.a317 L.sub.b8 1145 L.sub.a317 L.sub.b10 1146 L.sub.a317 L.sub.b12 1147 L.sub.a317 L.sub.b13 1148 L.sub.a317 L.sub.b17 1149 L.sub.a317 L.sub.b21 1150 L.sub.a317 L.sub.b22 1151 L.sub.a317 L.sub.b26 1152 L.sub.a317 L.sub.b28 1153 L.sub.a317 L.sub.b30 1154 L.sub.a317 L.sub.b31 1155 L.sub.a317 L.sub.b35 1156 L.sub.a317 L.sub.b37 1157 L.sub.a317 L.sub.b38 1158 L.sub.a317 L.sub.b39 1159 L.sub.a317 L.sub.b40 1160 L.sub.a317 L.sub.b41 1161 L.sub.a317 L.sub.b42 1162 L.sub.a317 L.sub.b43 1163 L.sub.a317 L.sub.b44 1164 L.sub.a317 L.sub.b45 1165 L.sub.a317 L.sub.b71 1166 L.sub.a317 L.sub.b72 1167 L.sub.a317 L.sub.b79 1168 L.sub.a317 L.sub.b80 1169 L.sub.a317 L.sub.b81 1170 L.sub.a317 L.sub.b99 1171 L.sub.a317 L.sub.b112 1172 L.sub.a317 L.sub.b151 1173 L.sub.a317 L.sub.b153 1174 L.sub.a317 L.sub.b164 1175 L.sub.a317 L.sub.b166 1176 L.sub.a317 L.sub.b209 1177 L.sub.a317 L.sub.b287 1178 L.sub.a317 L.sub.b299 1179 L.sub.a327 L.sub.b1 1180 L.sub.a327 L.sub.b3 1181 L.sub.a327 L.sub.b4 1182 L.sub.a327 L.sub.b8 1183 L.sub.a327 L.sub.b10 1184 L.sub.a327 L.sub.b12 1185 L.sub.a327 L.sub.b13 1186 L.sub.a327 L.sub.b17 1187 L.sub.a327 L.sub.b21 1188 L.sub.a327 L.sub.b22 1189 L.sub.a327 L.sub.b26 1190 L.sub.a327 L.sub.b28 1191 L.sub.a327 L.sub.b30 1192 L.sub.a327 L.sub.b31 1193 L.sub.a327 L.sub.b35 1194 L.sub.a327 L.sub.b37 1195 L.sub.a327 L.sub.b38 1196 L.sub.a327 L.sub.b39 1197 L.sub.a327 L.sub.b40 1198 L.sub.a327 L.sub.b41 1199 L.sub.a327 L.sub.b42 1200 L.sub.a327 L.sub.b43 1201 L.sub.a327 L.sub.b44 1202 L.sub.a327 L.sub.b45 1203 L.sub.a327 L.sub.b71 1204 L.sub.a327 L.sub.b72 1205 L.sub.a327 L.sub.b79 1206 L.sub.a327 L.sub.b80 1207 L.sub.a327 L.sub.b81 1208 L.sub.a327 L.sub.b99 1209 L.sub.a327 L.sub.b112 1210 L.sub.a327 L.sub.b151 1211 L.sub.a327 L.sub.b153 1212 L.sub.a327 L.sub.b164 1213 L.sub.a327 L.sub.b166 1214 L.sub.a327 L.sub.b209 1215 L.sub.a327 L.sub.b287 1216 L.sub.a327 L.sub.b299 1217 L.sub.a329 L.sub.b1 1218 L.sub.a329 L.sub.b3 1219 L.sub.a329 L.sub.b4 1220 L.sub.a329 L.sub.b8 1221 L.sub.a329 L.sub.b10 1222 L.sub.a329 L.sub.b12 1223 L.sub.a329 L.sub.b13 1224 L.sub.a329 L.sub.b17 1225 L.sub.a329 L.sub.b21 1226 L.sub.a329 L.sub.b22 1227 L.sub.a329 L.sub.b26 1228 L.sub.a329 L.sub.b28 1229 L.sub.a329 L.sub.b30 1230 L.sub.a329 L.sub.b31 1231 L.sub.a329 L.sub.b35 1232 L.sub.a329 L.sub.b37 1233 L.sub.a329 L.sub.b38 1234 L.sub.a329 L.sub.b39 1235 L.sub.a329 L.sub.b40 1236 L.sub.a329 L.sub.b41 1237 L.sub.a329 L.sub.b42 1238 L.sub.a329 L.sub.b43 1239 L.sub.a329 L.sub.b44 1240 L.sub.a329 L.sub.b45 1241 L.sub.a329 L.sub.b71 1242 L.sub.a329 L.sub.b72 1243 L.sub.a329 L.sub.b79 1244 L.sub.a329 L.sub.b80 1245 L.sub.a329 L.sub.b81 1246 L.sub.a329 L.sub.b99 1247 L.sub.a329 L.sub.b112 1248 L.sub.a329 L.sub.b151 1249 L.sub.a329 L.sub.b153 1250 L.sub.a329 L.sub.b164 1251 L.sub.a329 L.sub.b166 1252 L.sub.a329 L.sub.b209 1253 L.sub.a329 L.sub.b287 1254 L.sub.a329 L.sub.b299 1255 L.sub.a330 L.sub.b1 1256 L.sub.a330 L.sub.b3 1257 L.sub.a330 L.sub.b4 1258 L.sub.a330 L.sub.b8 1259 L.sub.a330 L.sub.b10 1260 L.sub.a330 L.sub.b12 1261 L.sub.a330 L.sub.b13 1262 L.sub.a330 L.sub.b17 1263 L.sub.a330 L.sub.b21 1264 L.sub.a330 L.sub.b22 1265 L.sub.a330 L.sub.b26 1266 L.sub.a330 L.sub.b28 1267 L.sub.a330 L.sub.b30 1268 L.sub.a330 L.sub.b31 1269 L.sub.a330 L.sub.b35 1270 L.sub.a330 L.sub.b37 1271 L.sub.a330 L.sub.b38 1272 L.sub.a330 L.sub.b39 1273 L.sub.a330 L.sub.b40 1274 L.sub.a330 L.sub.b41 1275 L.sub.a330 L.sub.b42 1276 L.sub.a330 L.sub.b43 1277 L.sub.a330 L.sub.b44 1278 L.sub.a330 L.sub.b45 1279 L.sub.a330 L.sub.b71 1280 L.sub.a330 L.sub.b72 1281 L.sub.a330 L.sub.b79 1282 L.sub.a330 L.sub.b80 1283 L.sub.a330 L.sub.b81 1284 L.sub.a330 L.sub.b99 1285 L.sub.a330 L.sub.b112 1286 L.sub.a330 L.sub.b151 1287 L.sub.a330 L.sub.b153 1288 L.sub.a330 L.sub.b164 1289 L.sub.a330 L.sub.b166 1290 L.sub.a330 L.sub.b209 1291 L.sub.a330 L.sub.b287 1292 L.sub.a330 L.sub.b299 1293 L.sub.a331 L.sub.b1 1294 L.sub.a331 L.sub.b3 1295 L.sub.a331 L.sub.b4 1296 L.sub.a331 L.sub.b8 1297 L.sub.a331 L.sub.b10 1298 L.sub.a331 L.sub.b12 1299 L.sub.a331 L.sub.b13 1300 L.sub.a331 L.sub.b17 1301 L.sub.a331 L.sub.b21 1302 L.sub.a331 L.sub.b22 1303 L.sub.a331 L.sub.b26 1304 L.sub.a331 L.sub.b28 1305 L.sub.a331 L.sub.b30 1306 L.sub.a331 L.sub.b31 1307 L.sub.a331 L.sub.b35 1308 L.sub.a331 L.sub.b37 1309 L.sub.a331 L.sub.b38 1310 L.sub.a331 L.sub.b39 1311 L.sub.a331 L.sub.b40 1312 L.sub.a331 L.sub.b41 1313 L.sub.a331 L.sub.b42 1314 L.sub.a331 L.sub.b43 1315 L.sub.a331 L.sub.b44 1316 L.sub.a331 L.sub.b45 1317 L.sub.a331 L.sub.b71 1318 L.sub.a331 L.sub.b72 1319 L.sub.a331 L.sub.b79 1320 L.sub.a331 L.sub.b80 1321 L.sub.a331 L.sub.b81 1322 L.sub.a331 L.sub.b99 1323 L.sub.a331 L.sub.b112 1324 L.sub.a331 L.sub.b151 1325 L.sub.a331 L.sub.b153 1326 L.sub.a331 L.sub.b164 1327 L.sub.a331 L.sub.b166 1328 L.sub.a331 L.sub.b209 1329 L.sub.a331 L.sub.b287 1330 L.sub.a331 L.sub.b299 1331 L.sub.a336 L.sub.b1 1332 L.sub.a336 L.sub.b3 1333 L.sub.a336 L.sub.b4 1334 L.sub.a336 L.sub.b8 1335 L.sub.a336 L.sub.b10 1336 L.sub.a336 L.sub.b12 1337 L.sub.a336 L.sub.b13 1338 L.sub.a336 L.sub.b17 1339 L.sub.a336 L.sub.b21 1340 L.sub.a336 L.sub.b22 1341 L.sub.a336 L.sub.b26 1342 L.sub.a336 L.sub.b28 1343 L.sub.a336 L.sub.b30 1344 L.sub.a336 L.sub.b31 1345 L.sub.a336 L.sub.b35 1346 L.sub.a336 L.sub.b37 1347 L.sub.a336 L.sub.b38 1348 L.sub.a336 L.sub.b39 1349 L.sub.a336 L.sub.b40 1350 L.sub.a336 L.sub.b41 1351 L.sub.a336 L.sub.b42 1352 L.sub.a336 L.sub.b43 1353 L.sub.a336 L.sub.b44 1354 L.sub.a336 L.sub.b45 1355 L.sub.a336 L.sub.b71 1356 L.sub.a336 L.sub.b72 1357 L.sub.a336 L.sub.b79 1358 L.sub.a336 L.sub.b80 1359 L.sub.a336 L.sub.b81 1360 L.sub.a336 L.sub.b99 1361 L.sub.a336 L.sub.b112 1362 L.sub.a336 L.sub.b151 1363 L.sub.a336 L.sub.b153 1364 L.sub.a336 L.sub.b164 1365 L.sub.a336 L.sub.b166 1366 L.sub.a336 L.sub.b209 1367 L.sub.a336 L.sub.b287 1368 L.sub.a336 L.sub.b299 1369 L.sub.a381 L.sub.b1 1370 L.sub.a381 L.sub.b3 1371 L.sub.a381 L.sub.b4 1372 L.sub.a381 L.sub.b8 1373 L.sub.a381 L.sub.b10 1374 L.sub.a381 L.sub.b12 1375 L.sub.a381 L.sub.b13 1376 L.sub.a381 L.sub.b17 1377 L.sub.a381 L.sub.b21 1378 L.sub.a381 L.sub.b22 1379 L.sub.a381 L.sub.b26 1380 L.sub.a381 L.sub.b28 1381 L.sub.a381 L.sub.b30 1382 L.sub.a381 L.sub.b31 1383 L.sub.a381 L.sub.b35 1384 L.sub.a381 L.sub.b37 1385 L.sub.a381 L.sub.b38 1386 L.sub.a381 L.sub.b39 1387 L.sub.a381 L.sub.b40 1388 L.sub.a381 L.sub.b41 1389 L.sub.a381 L.sub.b42 1390 L.sub.a381 L.sub.b43 1391 L.sub.a381 L.sub.b44 1392 L.sub.a381 L.sub.b45 1393 L.sub.a381 L.sub.b71 1394 L.sub.a381 L.sub.b72 1395 L.sub.a381 L.sub.b79 1396 L.sub.a381 L.sub.b80 1397 L.sub.a381 L.sub.b81 1398 L.sub.a381 L.sub.b99 1399 L.sub.a381 L.sub.b112 1400 L.sub.a381 L.sub.b151 1401 L.sub.a381 L.sub.b153 1402 L.sub.a381 L.sub.b164 1403 L.sub.a381 L.sub.b166 1404 L.sub.a381 L.sub.b209 1405 L.sub.a381 L.sub.b287 1406 L.sub.a381 L.sub.b299 1407 L.sub.a391 L.sub.b1 1408 L.sub.a391 L.sub.b3 1409 L.sub.a391 L.sub.b4 1410 L.sub.a391 L.sub.b8 1411 L.sub.a391 L.sub.b10 1412 L.sub.a391 L.sub.b12 1413 L.sub.a391 L.sub.b13 1414 L.sub.a391 L.sub.b17 1415 L.sub.a391 L.sub.b21 1416 L.sub.a391 L.sub.b22 1417 L.sub.a391 L.sub.b26 1418 L.sub.a391 L.sub.b28 1419 L.sub.a391 L.sub.b30 1420 L.sub.a391 L.sub.b31 1421 L.sub.a391 L.sub.b35 1422 L.sub.a391 L.sub.b37 1423 L.sub.a391 L.sub.b38 1424 L.sub.a391 L.sub.b39 1425 L.sub.a391 L.sub.b40 1426 L.sub.a391 L.sub.b41 1427 L.sub.a391 L.sub.b42 1428 L.sub.a391 L.sub.b43 1429 L.sub.a391 L.sub.b44 1430 L.sub.a391 L.sub.b45 1431 L.sub.a391 L.sub.b71 1432 L.sub.a391 L.sub.b72 1433 L.sub.a391 L.sub.b79 1434 L.sub.a391 L.sub.b80 1435 L.sub.a391 L.sub.b81 1436 L.sub.a391 L.sub.b99 1437 L.sub.a391 L.sub.b112 1438 L.sub.a391 L.sub.b151 1439 L.sub.a391 L.sub.b153 1440 L.sub.a391 L.sub.b164 1441 L.sub.a391 L.sub.b166 1442 L.sub.a391 L.sub.b209 1443 L.sub.a391 L.sub.b287 1444 L.sub.a391 L.sub.b299 1445 L.sub.a403 L.sub.b1 1446 L.sub.a403 L.sub.b3 1447 L.sub.a403 L.sub.b4 1448 L.sub.a403 L.sub.b8 1449 L.sub.a403 L.sub.b10 1450 L.sub.a403 L.sub.b12 1451 L.sub.a403 L.sub.b13 1452 L.sub.a403 L.sub.b17 1453 L.sub.a403 L.sub.b21 1454 L.sub.a403 L.sub.b22 1455 L.sub.a403 L.sub.b26 1456 L.sub.a403 L.sub.b28 1457 L.sub.a403 L.sub.b30 1458 L.sub.a403 L.sub.b31 1459 L.sub.a403 L.sub.b35 1460 L.sub.a403 L.sub.b37 1461 L.sub.a403 L.sub.b38 1462 L.sub.a403 L.sub.b39 1463 L.sub.a403 L.sub.b40 1464 L.sub.a403 L.sub.b41 1465 L.sub.a403 L.sub.b42 1466 L.sub.a403 L.sub.b43 1467 L.sub.a403 L.sub.b44 1468 L.sub.a403 L.sub.b45 1469 L.sub.a403 L.sub.b71 1470 L.sub.a403 L.sub.b72 1471 L.sub.a403 L.sub.b79 1472 L.sub.a403 L.sub.b80 1473 L.sub.a403 L.sub.b81 1474 L.sub.a403 L.sub.b99 1475 L.sub.a403 L.sub.b112 1476 L.sub.a403 L.sub.b151 1477 L.sub.a403 L.sub.b153 1478 L.sub.a403 L.sub.b164 1479 L.sub.a403 L.sub.b166 1480 L.sub.a403 L.sub.b209 1481 L.sub.a403 L.sub.b287 1482 L.sub.a403 L.sub.b299 1483 L.sub.a413 L.sub.b1 1484 L.sub.a413 L.sub.b3 1485 L.sub.a413 L.sub.b4 1486 L.sub.a413 L.sub.b8 1487 L.sub.a413 L.sub.b10 1488 L.sub.a413 L.sub.b12 1489 L.sub.a413 L.sub.b13 1490 L.sub.a413 L.sub.b17 1491 L.sub.a413 L.sub.b21 1492 L.sub.a413 L.sub.b22 1493 L.sub.a413 L.sub.b26 1494 L.sub.a413 L.sub.b28 1495 L.sub.a413 L.sub.b30 1496 L.sub.a413 L.sub.b31 1497 L.sub.a413 L.sub.b35 1498 L.sub.a413 L.sub.b37 1499 L.sub.a413 L.sub.b38 1500 L.sub.a413 L.sub.b39 1501 L.sub.a413 L.sub.b40 1502 L.sub.a413 L.sub.b41 1503 L.sub.a413 L.sub.b42 1504 L.sub.a413 L.sub.b43 1505 L.sub.a413 L.sub.b44 1506 L.sub.a413 L.sub.b45 1507 L.sub.a413 L.sub.b71 1508 L.sub.a413 L.sub.b72 1509 L.sub.a413 L.sub.b79 1510 L.sub.a413 L.sub.b80 1511 L.sub.a413 L.sub.b81 1512 L.sub.a413 L.sub.b99 1513 L.sub.a413 L.sub.b112 1514 L.sub.a413 L.sub.b151 1515 L.sub.a413 L.sub.b153 1516 L.sub.a413 L.sub.b164 1517 L.sub.a413 L.sub.b166 1518 L.sub.a413 L.sub.b209 1519 L.sub.a413 L.sub.b287 1520 L.sub.a413 L.sub.b299 1521 L.sub.a435 L.sub.b1 1522 L.sub.a435 L.sub.b3 1523 L.sub.a435 L.sub.b4 1524 L.sub.a435 L.sub.b8 1525 L.sub.a435 L.sub.b10 1526 L.sub.a435 L.sub.b12 1527 L.sub.a435 L.sub.b13 1528 L.sub.a435 L.sub.b17 1529 L.sub.a435 L.sub.b21 1530 L.sub.a435 L.sub.b22 1531 L.sub.a435 L.sub.b26 1532 L.sub.a435 L.sub.b28 1533 L.sub.a435 L.sub.b30 1534 L.sub.a435 L.sub.b31 1535 L.sub.a435 L.sub.b35 1536 L.sub.a435 L.sub.b37 1537 L.sub.a435 L.sub.b38 1538 L.sub.a435 L.sub.b39 1539 L.sub.a435 L.sub.b40 1540 L.sub.a435 L.sub.b41 1541 L.sub.a435 L.sub.b42 1542 L.sub.a435 L.sub.b43 1543 L.sub.a435 L.sub.b44 1544 L.sub.a435 L.sub.b45 1545 L.sub.a435 L.sub.b71 1546 L.sub.a435 L.sub.b72 1547 L.sub.a435 L.sub.b79 1548 L.sub.a435 L.sub.b80 1549 L.sub.a435 L.sub.b81 1550 L.sub.a435 L.sub.b99 1551 L.sub.a435 L.sub.b112 1552 L.sub.a435 L.sub.b151 1553 L.sub.a435 L.sub.b153 1554 L.sub.a435 L.sub.b164 1555 L.sub.a435 L.sub.b166 1556 L.sub.a435 L.sub.b209 1557 L.sub.a435 L.sub.b287 1558 L.sub.a435 L.sub.b299 1559 L.sub.a446 L.sub.b1 1560 L.sub.a446 L.sub.b3 1561 L.sub.a446 L.sub.b4 1562 L.sub.a446 L.sub.b8 1563 L.sub.a446 L.sub.b10 1564 L.sub.a446 L.sub.b12 1565 L.sub.a446 L.sub.b13 1566 L.sub.a446 L.sub.b17 1567 L.sub.a446 L.sub.b21 1568 L.sub.a446 L.sub.b22 1569 L.sub.a446 L.sub.b26 1570 L.sub.a446 L.sub.b28 1571 L.sub.a446 L.sub.b30 1572 L.sub.a446 L.sub.b31 1573 L.sub.a446 L.sub.b35 1574 L.sub.a446 L.sub.b37 1575 L.sub.a446 L.sub.b38 1576 L.sub.a446 L.sub.b39 1577 L.sub.a446 L.sub.b40 1578 L.sub.a446 L.sub.b41 1579 L.sub.a446 L.sub.b42 1580 L.sub.a446 L.sub.b43 1581 L.sub.a446 L.sub.b44 1582 L.sub.a446 L.sub.b45 1583 L.sub.a446 L.sub.b71 1584 L.sub.a446 L.sub.b72 1585 L.sub.a446 L.sub.b79 1586 L.sub.a446 L.sub.b80 1587 L.sub.a446 L.sub.b81 1588 L.sub.a446 L.sub.b99 1589 L.sub.a446 L.sub.b112 1590 L.sub.a446 L.sub.b151 1591 L.sub.a446 L.sub.b153 1592 L.sub.a446 L.sub.b164 1593 L.sub.a446 L.sub.b166 1594 L.sub.a446 L.sub.b209 1595 L.sub.a446 L.sub.b287 1596 L.sub.a446 L.sub.b299 1597 L.sub.a466 L.sub.b1 1598 L.sub.a466 L.sub.b3 1599 L.sub.a466 L.sub.b4 1600 L.sub.a466 L.sub.b8 1601 L.sub.a466 L.sub.b10 1602 L.sub.a466 L.sub.b12 1603 L.sub.a466 L.sub.b13 1604 L.sub.a466 L.sub.b17 1605 L.sub.a466 L.sub.b21 1606 L.sub.a466 L.sub.b22 1607 L.sub.a466 L.sub.b26 1608 L.sub.a466 L.sub.b28 1609 L.sub.a466 L.sub.b30 1610 L.sub.a466 L.sub.b31 1611 L.sub.a466 L.sub.b35 1612 L.sub.a466 L.sub.b37 1613 L.sub.a466 L.sub.b38 1614 L.sub.a466 L.sub.b39 1615 L.sub.a466 L.sub.b40 1616 L.sub.a466 L.sub.b41 1617 L.sub.a466 L.sub.b42 1618 L.sub.a466 L.sub.b43 1619 L.sub.a466 L.sub.b44 1620 L.sub.a466 L.sub.b45 1621 L.sub.a466 L.sub.b71 1622 L.sub.a466 L.sub.b72 1623 L.sub.a466 L.sub.b79 1624 L.sub.a466 L.sub.b80 1625 L.sub.a466 L.sub.b81 1626 L.sub.a466 L.sub.b99 1627 L.sub.a466 L.sub.b112 1628 L.sub.a466 L.sub.b151 1629 L.sub.a466 L.sub.b153 1630 L.sub.a466 L.sub.b164 1631 L.sub.a466 L.sub.b166 1632 L.sub.a466 L.sub.b209 1633 L.sub.a466 L.sub.b287 1634 L.sub.a466 L.sub.b299 1635 L.sub.a518 L.sub.b1 1636 L.sub.a518 L.sub.b3 1637 L.sub.a518 L.sub.b4 1638 L.sub.a518 L.sub.b8 1639 L.sub.a518 L.sub.b10 1640 L.sub.a518 L.sub.b12 1641 L.sub.a518 L.sub.b13 1642 L.sub.a518 L.sub.b17 1643 L.sub.a518 L.sub.b21 1644 L.sub.a518 L.sub.b22 1645 L.sub.a518 L.sub.b26 1646 L.sub.a518 L.sub.b28 1647 L.sub.a518 L.sub.b30 1648 L.sub.a518 L.sub.b31 1649 L.sub.a518 L.sub.b35 1650 L.sub.a518 L.sub.b37 1651 L.sub.a518 L.sub.b38 1652 L.sub.a518 L.sub.b39 1653 L.sub.a518 L.sub.b40 1654 L.sub.a518 L.sub.b41 1655 L.sub.a518 L.sub.b42 1656 L.sub.a518 L.sub.b43 1657 L.sub.a518 L.sub.b44 1658 L.sub.a518 L.sub.b45 1659 L.sub.a518 L.sub.b71 1660 L.sub.a518 L.sub.b72 1661 L.sub.a518 L.sub.b79 1662 L.sub.a518 L.sub.b80 1663 L.sub.a518 L.sub.b81 1664 L.sub.a518 L.sub.b99 1665 L.sub.a518 L.sub.b112 1666 L.sub.a518 L.sub.b151 1667 L.sub.a518 L.sub.b153 1668 L.sub.a518 L.sub.b164 1669 L.sub.a518 L.sub.b166 1670 L.sub.a518 L.sub.b209 1671 L.sub.a518 L.sub.b287 1672 L.sub.a518 L.sub.b299 1673 L.sub.a519 L.sub.b1 1674 L.sub.a519 L.sub.b3 1675 L.sub.a519 L.sub.b4 1676 L.sub.a519 L.sub.b8 1677 L.sub.a519 L.sub.b10 1678 L.sub.a519 L.sub.b12 1679 L.sub.a519 L.sub.b13 1680 L.sub.a519 L.sub.b17 1681 L.sub.a519 L.sub.b21 1682 L.sub.a519 L.sub.b22 1683 L.sub.a519 L.sub.b26 1684 L.sub.a519 L.sub.b28 1685 L.sub.a519 L.sub.b30 1686 L.sub.a519 L.sub.b31 1687 L.sub.a519 L.sub.b35 1688 L.sub.a519 L.sub.b37 1689 L.sub.a519 L.sub.b38 1690 L.sub.a519 L.sub.b39 1691 L.sub.a519 L.sub.b40 1692 L.sub.a519 L.sub.b41 1693 L.sub.a519 L.sub.b42 1694 L.sub.a519 L.sub.b43 1695 L.sub.a519 L.sub.b44 1696 L.sub.a519 L.sub.b45 1697 L.sub.a519 L.sub.b71 1698 L.sub.a519 L.sub.b72 1699 L.sub.a519 L.sub.b79 1700 L.sub.a519 L.sub.b80 1701 L.sub.a519 L.sub.b81 1702 L.sub.a519 L.sub.b99 1703 L.sub.a519 L.sub.b112 1704 L.sub.a519 L.sub.b151 1705 L.sub.a519 L.sub.b153 1706 L.sub.a519 L.sub.b164 1707 L.sub.a519 L.sub.b166 1708 L.sub.a519 L.sub.b209 1709 L.sub.a519 L.sub.b287 1710 L.sub.a519 L.sub.b299 1711 L.sub.a525 L.sub.b1 1712 L.sub.a525 L.sub.b3 1713 L.sub.a525 L.sub.b4 1714 L.sub.a525 L.sub.b8 1715 L.sub.a525 L.sub.b10 1716 L.sub.a525 L.sub.b12 1717 L.sub.a525 L.sub.b13 1718 L.sub.a525 L.sub.b17 1719 L.sub.a525 L.sub.b21 1720 L.sub.a525 L.sub.b22 1721 L.sub.a525 L.sub.b26 1722 L.sub.a525 L.sub.b28 1723 L.sub.a525 L.sub.b30 1724 L.sub.a525 L.sub.b31 1725 L.sub.a525 L.sub.b35 1726 L.sub.a525 L.sub.b37 1727 L.sub.a525 L.sub.b38 1728 L.sub.a525 L.sub.b39 1729 L.sub.a525 L.sub.b40 1730 L.sub.a525 L.sub.b41 1731 L.sub.a525 L.sub.b42 1732 L.sub.a525 L.sub.b43 1733 L.sub.a525 L.sub.b44 1734 L.sub.a525 L.sub.b45 1735 L.sub.a525 L.sub.b71 1736 L.sub.a525 L.sub.b72 1737 L.sub.a525 L.sub.b79 1738 L.sub.a525 L.sub.b80 1739 L.sub.a525 L.sub.b81 1740 L.sub.a525 L.sub.b99 1741 L.sub.a525 L.sub.b112 1742 L.sub.a525 L.sub.b151 1743 L.sub.a525 L.sub.b153 1744 L.sub.a525 L.sub.b164 1745 L.sub.a525 L.sub.b166 1746 L.sub.a525 L.sub.b209 1747 L.sub.a525 L.sub.b287 1748 L.sub.a525 L.sub.b299 1749 L.sub.a562 L.sub.b1 1750 L.sub.a562 L.sub.b3 1751 L.sub.a562 L.sub.b4 1752 L.sub.a562 L.sub.b8 1753 L.sub.a562 L.sub.b10 1754 L.sub.a562 L.sub.b12 1755 L.sub.a562 L.sub.b13 1756 L.sub.a562 L.sub.b17 1757 L.sub.a562 L.sub.b21 1758 L.sub.a562 L.sub.b22 1759 L.sub.a562 L.sub.b26 1760 L.sub.a562 L.sub.b28 1761 L.sub.a562 L.sub.b30 1762 L.sub.a562 L.sub.b31 1763 L.sub.a562 L.sub.b35 1764 L.sub.a562 L.sub.b37 1765 L.sub.a562 L.sub.b38 1766 L.sub.a562 L.sub.b39 1767 L.sub.a562 L.sub.b40 1768 L.sub.a562 L.sub.b41 1769 L.sub.a562 L.sub.b42 1770 L.sub.a562 L.sub.b43 1771 L.sub.a562 L.sub.b44 1772 L.sub.a562 L.sub.b45 1773 L.sub.a562 L.sub.b71 1774 L.sub.a562 L.sub.b72 1775 L.sub.a562 L.sub.b79 1776 L.sub.a562 L.sub.b80 1777 L.sub.a562 L.sub.b81 1778 L.sub.a562 L.sub.b99 1779 L.sub.a562 L.sub.b112 1780 L.sub.a562 L.sub.b151 1781 L.sub.a562 L.sub.b153 1782 L.sub.a562 L.sub.b164 1783 L.sub.a562 L.sub.b166 1784 L.sub.a562 L.sub.b209 1785 L.sub.a562 L.sub.b287 1786 L.sub.a562 L.sub.b299 1787 L.sub.a575 L.sub.b1 1788 L.sub.a575 L.sub.b3 1789 L.sub.a575 L.sub.b4 1790 L.sub.a575 L.sub.b8 1791 L.sub.a575 L.sub.b10 1792 L.sub.a575 L.sub.b12 1793 L.sub.a575 L.sub.b13 1794 L.sub.a575 L.sub.b17 1795 L.sub.a575 L.sub.b21 1796 L.sub.a575 L.sub.b22 1797 L.sub.a575 L.sub.b26 1798 L.sub.a575 L.sub.b28 1799 L.sub.a575 L.sub.b30 1800 L.sub.a575 L.sub.b31 1801 L.sub.a575 L.sub.b35 1802 L.sub.a575 L.sub.b37 1803 L.sub.a575 L.sub.b38 1804 L.sub.a575 L.sub.b39 1805 L.sub.a575 L.sub.b40 1806 L.sub.a575 L.sub.b41 1807 L.sub.a575 L.sub.b42 1808 L.sub.a575 L.sub.b43 1809 L.sub.a575 L.sub.b44 1810 L.sub.a575 L.sub.b45 1811 L.sub.a575 L.sub.b71 1812 L.sub.a575 L.sub.b72 1813 L.sub.a575 L.sub.b79 1814 L.sub.a575 L.sub.b80 1815 L.sub.a575 L.sub.b81 1816 L.sub.a575 L.sub.b99 1817 L.sub.a575 L.sub.b112 1818 L.sub.a575 L.sub.b151 1819 L.sub.a575 L.sub.b153 1820 L.sub.a575 L.sub.b164 1821 L.sub.a575 L.sub.b166 1822 L.sub.a575 L.sub.b209 1823 L.sub.a575 L.sub.b287 1824 L.sub.a575 L.sub.b299 1825 L.sub.a584 L.sub.b1 1826 L.sub.a584 L.sub.b3 1827 L.sub.a584 L.sub.b4 1828 L.sub.a584 L.sub.b8 1829 L.sub.a584 L.sub.b10 1830 L.sub.a584 L.sub.b12 1831 L.sub.a584 L.sub.b13 1832 L.sub.a584 L.sub.b17 1833 L.sub.a584 L.sub.b21 1834 L.sub.a584 L.sub.b22 1835 L.sub.a584 L.sub.b26 1836 L.sub.a584 L.sub.b28 1837 L.sub.a584 L.sub.b30 1838 L.sub.a584 L.sub.b31 1839 L.sub.a584 L.sub.b35 1840 L.sub.a584 L.sub.b37 1841 L.sub.a584 L.sub.b38 1842 L.sub.a584 L.sub.b39 1843 L.sub.a584 L.sub.b40 1844 L.sub.a584 L.sub.b41 1845 L.sub.a584 L.sub.b42 1846 L.sub.a584 L.sub.b43 1847 L.sub.a584 L.sub.b44 1848 L.sub.a584 L.sub.b45 1849 L.sub.a584 L.sub.b71 1850 L.sub.a584 L.sub.b72 1851 L.sub.a584 L.sub.b79 1852 L.sub.a584 L.sub.b80 1853 L.sub.a584 L.sub.b81 1854 L.sub.a584 L.sub.b99 1855 L.sub.a584 L.sub.b112 1856 L.sub.a584 L.sub.b151 1857 L.sub.a584 L.sub.b153 1858 L.sub.a584 L.sub.b164 1859 L.sub.a584 L.sub.b166 1860 L.sub.a584 L.sub.b209 1861 L.sub.a584 L.sub.b287 1862 L.sub.a584 L.sub.b299 1863 L.sub.a597 L.sub.b1 1864 L.sub.a597 L.sub.b3 1865 L.sub.a597 L.sub.b4 1866 L.sub.a597 L.sub.b8 1867 L.sub.a597 L.sub.b10 1868 L.sub.a597 L.sub.b12 1869 L.sub.a597 L.sub.b13 1870 L.sub.a597 L.sub.b17 1871 L.sub.a597 L.sub.b21 1872 L.sub.a597 L.sub.b22 1873 L.sub.a597 L.sub.b26 1874 L.sub.a597 L.sub.b28 1875 L.sub.a597 L.sub.b30 1876 L.sub.a597 L.sub.b31 1877 L.sub.a597 L.sub.b35 1878 L.sub.a597 L.sub.b37 1879 L.sub.a597 L.sub.b38 1880 L.sub.a597 L.sub.b39 1881 L.sub.a597 L.sub.b40 1882 L.sub.a597 L.sub.b41 1883 L.sub.a597 L.sub.b42 1884 L.sub.a597 L.sub.b43 1885 L.sub.a597 L.sub.b44 1886 L.sub.a597 L.sub.b45 1887 L.sub.a597 L.sub.b71 1888 L.sub.a597 L.sub.b72 1889 L.sub.a597 L.sub.b79 1890 L.sub.a597 L.sub.b80 1891 L.sub.a597 L.sub.b81 1892 L.sub.a597 L.sub.b99 1893 L.sub.a597 L.sub.b112 1894 L.sub.a597 L.sub.b151 1895 L.sub.a597 L.sub.b153 1896 L.sub.a597 L.sub.b164 1897 L.sub.a597 L.sub.b166 1898 L.sub.a597 L.sub.b209 1899 L.sub.a597 L.sub.b287 1900 L.sub.a597 L.sub.b299 1901 L.sub.a10 L.sub.b3 1902 L.sub.a10 L.sub.b81.
21. An electroluminescent device, comprising: an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises the metal complex of claim 1.
22. The electroluminescent device of claim 21, wherein the organic layer comprising the metal complex is an emissive layer.
23. The electroluminescent device of claim 22, wherein the electroluminescent device emits green light or white light.
24. The electroluminescent device of claim 22, wherein the emissive layer comprises a first host compound; preferably, the emissive layer further comprises a second host compound; more preferably, the first host compound and/or the second host compound comprise at least one chemical group selected from the group consisting of: benzene, pyridine, pyrimidine, triazine, carbazole, azacarbazole, indolocarbazole, dibenzothiophene, azadibenzothiophene, dibenzofuran, azadibenzofuran, dibenzoselenophene, triphenylene, azatriphenylene, fluorene, silafluorene, naphthalene, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene, azaphenanthrene, and combinations thereof.
25. The electroluminescent device of claim 24, wherein the first host compound has a structure represented by Formula 4: ##STR00469## wherein, E.sub.1 to E.sub.6 are, at each occurrence identically or differently, selected from C, CR.sub.e or N, at least two of E.sub.1 to E.sub.6 are N, and at least one of E.sub.1 to E.sub.6 is C and is attached to Formula A: ##STR00470## wherein, Q is, at each occurrence identically or differently, selected from the group consisting of O, S, Se, N, NR′″, CR′″R′″, Si′″R′″, GeR′″R′″, and R′″C═CR′″; when two R′″ are present, the two R′″ can be identical or different; p is 0 or 1; r is 0 or 1; when Q is selected from N, p is 0, and r is 1; when Q is selected from the group consisting of O, S, Se, NR′″, CR′″R′″, SiR′″R′″, GeR′″R′″, and R′″C═CR′″, p is 1, and r is 0; L is, at each occurrence identically or differently, selected from a single bond, substituted or unsubstituted alkylene having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkylene having 3 to 20 carbon atoms, substituted or unsubstituted arylene having 6 to 20 carbon atoms, substituted or unsubstituted heteroarylene having 3 to 20 carbon atoms or combinations thereof; Q.sub.1 to Q.sub.8 are, at each occurrence identically or differently, selected from C, CR.sub.q or N; R.sub.e, R′″, and R.sub.q are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof; “*” represents a position where Formula A is attached to Formula 4; adjacent substituents R.sub.e, R′″, R.sub.q can be optionally joined to form a ring.
26. The electroluminescent device of claim 25, wherein E.sub.1 to E.sub.6 are, at each occurrence identically or differently, selected from C, CR.sub.e or N; wherein three of E.sub.1 to E.sub.6 are N, and at least one of E.sub.1 to E.sub.6 is CR.sub.e wherein the R.sub.e is, at each occurrence identically or differently, selected from the group consisting of: substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, and combinations thereof; and/or Q is, at each occurrence identically or differently, selected from O, S, N or NR″; and/or R′″ 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; and/or at least one or at least two of Q.sub.1 to Q.sub.8 is(are) selected from CR.sub.q, wherein the R.sub.q is selected from substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 5 to 30 carbon atoms or combinations thereof; and/or L is, at each occurrence identically or differently, selected from a single bond, substituted or unsubstituted arylene having 6 to 20 carbon atoms, substituted or unsubstituted heteroarylene having 3 to 20 carbon atoms or combinations thereof.
27. The electroluminescent device of claim 25, wherein the first host compound is selected from the group consisting of: ##STR00471## ##STR00472## ##STR00473## ##STR00474## ##STR00475## ##STR00476## ##STR00477## ##STR00478## ##STR00479## ##STR00480## ##STR00481## ##STR00482## ##STR00483## ##STR00484## ##STR00485## ##STR00486## ##STR00487## ##STR00488## ##STR00489## ##STR00490## ##STR00491## ##STR00492## ##STR00493## ##STR00494## ##STR00495## ##STR00496## ##STR00497## ##STR00498## ##STR00499## ##STR00500## ##STR00501## ##STR00502## ##STR00503## ##STR00504## ##STR00505## ##STR00506## ##STR00507## ##STR00508## ##STR00509## ##STR00510## ##STR00511##
28. The electroluminescent device of claim 24, wherein the second host compound has a structure represented by Formula 5: ##STR00512## wherein, L.sub.x is, at each occurrence identically or differently, selected from a single bond, substituted or unsubstituted alkylene having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkylene having 3 to 20 carbon atoms, substituted or unsubstituted arylene having 6 to 20 carbon atoms, substituted or unsubstituted heteroarylene having 3 to 20 carbon atoms or combinations thereof; V is, at each occurrence identically or differently, selected from C, CR.sub.v or N, and at least one of V is C and is attached to L.sub.x; U is, at each occurrence identically or differently, selected from C, CR.sub.u or N, and at least one of U is C and is attached to L.sub.x; R.sub.v and R.sub.u are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof; Ar.sub.6 is, at each occurrence identically or differently, selected from substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms or combinations thereof; adjacent substituents R.sub.v and R.sub.u can be optionally joined to form a ring; preferably, the second host compound has a structure represented by one of Formula 5-a to Formula 5-j: ##STR00513## ##STR00514##
29. The electroluminescent device of claim 28, wherein the second host compound is selected from the group consisting of: ##STR00515## ##STR00516## ##STR00517## ##STR00518## ##STR00519## ##STR00520## ##STR00521## ##STR00522## ##STR00523## ##STR00524## ##STR00525## ##STR00526## ##STR00527## ##STR00528## ##STR00529## ##STR00530## ##STR00531## ##STR00532## ##STR00533## ##STR00534## ##STR00535## ##STR00536## ##STR00537## ##STR00538## ##STR00539## ##STR00540## ##STR00541## ##STR00542## ##STR00543## ##STR00544## ##STR00545## ##STR00546## ##STR00547## ##STR00548## ##STR00549## ##STR00550## ##STR00551## ##STR00552## ##STR00553## ##STR00554## ##STR00555## ##STR00556## ##STR00557## ##STR00558## ##STR00559## ##STR00560## ##STR00561## ##STR00562## ##STR00563## ##STR00564## ##STR00565## ##STR00566## ##STR00567## ##STR00568## ##STR00569## ##STR00570## ##STR00571## ##STR00572## ##STR00573## ##STR00574## ##STR00575## ##STR00576##
30. The electroluminescent device of claim 24, 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; preferably, the weight of the metal complex accounts for 3% to 13% of the total weight of the emissive layer.
31. A compound composition, comprising the metal complex of claim 1.
Description
BRIEF DESCRIPTION OF DRAWINGS
[0036]
[0037]
DETAILED DESCRIPTION
[0038] OLEDs can be fabricated on various types of substrates such as glass, plastic, and metal foil.
[0039] 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.
[0040] 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.
[0041] 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.
[0042] An OLED can be encapsulated by a barrier layer.
[0043] 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.
[0044] The materials and structures described herein may be used in other organic electronic devices listed above.
[0045] 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.
[0046] 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.
[0047] 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.
[0048] 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).
[0049] 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.
[0050] 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 (A.sub.ES-T). Organic, non-metal containing, donor-acceptor luminescent materials may be able to achieve this. The emission in these materials is generally characterized as a donor-acceptor charge-transfer (CT) type emission. The spatial separation of the HOMO and LUMO in these donor-acceptor type compounds generally results in small Δ.sub.ES-T. These states may involve CT states. Generally, donor-acceptor luminescent materials are constructed by connecting an electron donor moiety such as amino- or carbazole-derivatives and an electron acceptor moiety such as N-containing six-membered aromatic rings.
[0051] Definition of Terms of Substituents
[0052] Halogen or halide—as used herein includes fluorine, chlorine, bromine, and iodine.
[0053] Alkyl—as used herein includes both straight and branched chain alkyl groups. Alkyl may be alkyl having 1 to 20 carbon atoms, preferably alkyl having 1 to 12 carbon atoms, and more preferably alkyl having 1 to 6 carbon atoms. Examples of alkyl groups include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an s-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, a neopentyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 1-pentylhexyl group, a 1-butylpentyl group, a 1-heptyloctyl group, and a 3-methylpentyl group. Of the above, preferred are a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an s-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, a neopentyl group, and an n-hexyl group. Additionally, the alkyl group may be optionally substituted.
[0054] 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.
[0055] 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.
[0056] 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.
[0057] 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.
[0058] 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.
[0059] Heterocyclic groups or heterocycle—as used herein include non-aromatic cyclic groups. Non-aromatic heterocyclic groups includes saturated heterocyclic groups having 3 to 20 ring atoms and unsaturated non-aromatic heterocyclic groups having 3 to 20 ring atoms, where at least one ring atom is selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, a silicon atom, a phosphorus atom, a germanium atom, and a boron atom. Preferred non-aromatic heterocyclic groups are those having 3 to 7 ring atoms, each of which includes at least one hetero-atom such as nitrogen, oxygen, silicon, or sulfur. Examples of non-aromatic heterocyclic groups include oxiranyl, oxetanyl, tetrahydrofuranyl, tetrahydropyranyl, dioxolanyl, dioxanyl, aziridinyl, dihydropyrrolyl, tetrahydropyrrolyl, piperidinyl, oxazolidinyl, morpholinyl, piperazinyl, oxepinyl, thiepinyl, azepinyl, and tetrahydrosilolyl. Additionally, the heterocyclic group may be optionally substituted.
[0060] 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.
[0061] 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.
[0062] 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.
[0063] 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.
[0064] 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.
[0065] 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.
[0066] 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.
[0067] 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.
[0068] 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.
[0069] 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.
[0070] 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.
[0071] 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.
[0072] 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.
[0073] 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.
[0074] 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:
##STR00009##
[0075] 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:
##STR00010##
[0076] 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:
##STR00011##
[0077] 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:
##STR00012##
[0078] According to an embodiment of the present disclosure, a metal complex is disclosed. The metal complex comprises a metal M and a ligand L.sub.a coordinated to the metal M, wherein the metal M is selected from metals having a relative atomic mass greater than 40, and L.sub.a has a structure represented by Formula 1:
##STR00013##
[0079] wherein in Formula 1,
[0080] 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 combinations thereof;
[0081] X is selected from the group consisting of O, S, Se, NR′, CR′R′, SiR′R′, and GeR′R′; when two R′ are present, the two R′ are identical or different;
[0082] X.sub.1 to X.sub.7 are, at each occurrence identically or differently, selected from C, CR.sub.x or N; at least one of X.sub.1 to X.sub.4 is C and is attached to Cy;
[0083] X.sub.1, X.sub.2, X.sub.3 or X.sub.4 is attached to the metal M through a metal-carbon bond or a metal-nitrogen bond;
[0084] at least one of X.sub.1 to X.sub.7 is CR.sub.x, wherein the R.sub.x is cyano or fluorine;
[0085] A has a structure represented by Formula 2:
##STR00014##
[0086] wherein a is selected from 1, 2, 3, 4 or 5;
[0087] A.sub.1 is, at each occurrence identically or differently, selected from the group consisting of: O, S, Se, NR″, SiR″R″, GeR″R″, BR″, PR″, P(O)R″, following groups unsubstituted or substituted by one or at least two R.sub.a1: alkylene having 1 to 20 carbon atoms, heteroalkylene having 1 to 20 carbon atoms, cycloalkylene having 3 to 20 carbon atoms, heterocyclene having 3 to 20 ring atoms, arylene having 6 to 30 carbon atoms and heteroarylene having 3 to 30 carbon atoms, and combinations thereof;
[0088] A.sub.2 is, at each occurrence identically or differently, selected from the group consisting of: O, S, Se, NR″, SiR″R″, GeR″R″, BR″, PR″, P(O)R″, following groups unsubstituted or substituted by one or at least two R.sub.a2: alkylene having 1 to 20 carbon atoms, heteroalkylene having 1 to 20 carbon atoms, cycloalkylene having 3 to 20 carbon atoms, heterocyclene having 3 to 20 ring atoms, arylene having 6 to 30 carbon atoms and heteroarylene having 3 to 30 carbon atoms, and combinations thereof;
[0089] R′, R″, R.sub.x, 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 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;
[0090] adjacent substituents R′, R″, R.sub.x, R.sub.a1, R.sub.a2, R.sub.a3 can be optionally joined to form a ring;
[0091] the length of A is at least 6.7 Å;
[0092] “*” represents a position where A is attached.
[0093] According to an embodiment of the present disclosure, a metal complex is disclosed. The metal complex comprises a metal M and a ligand L.sub.a coordinated to the metal M, wherein the metal M is selected from metals having a relative atomic mass greater than 40, and L.sub.a has a structure represented by Formula 1:
##STR00015##
wherein in Formula 1,
Cy is, at each occurrence identically or differently, selected from a substituted or unsubstituted aromatic ring having 6 to 24 ring atoms, a substituted or unsubstituted heteroaromatic ring having 5 to 24 ring atoms or combinations thereof;
X is selected from the group consisting of O, S, Se, NR′, CR′R′, SiR′R′, and GeR′R′; when two R′ are present, the two R′ are identical or different;
X.sub.1 to X.sub.7 are, at each occurrence identically or differently, selected from C, CR.sub.x or N; at least one of X.sub.1 to X.sub.4 is C and is attached to Cy;
X.sub.1, X.sub.2, X.sub.3 or X.sub.4 is attached to the metal M through a metal-carbon bond or a metal-nitrogen bond;
at least one of X.sub.1 to X.sub.7 is CR.sub.x, wherein the R.sub.x, is a cyano group or fluorine;
A has a structure represented by Formula 2:
##STR00016##
wherein a is selected from 1, 2, 3, 4 or 5;
A.sub.1 is, at each occurrence identically or differently, selected from the group consisting of: O, S, Se, NR″, SiR″R″, GeR″R″, BR″, PR″, P(O)R″, following groups unsubstituted or substituted by one or at least two R.sub.a1: alkylene having 1 to 20 carbon atoms, heteroalkylene having 1 to 20 carbon atoms, cycloalkylene having 3 to 20 carbon atoms, heterocyclene having 3 to 20 ring atoms, phenylene and heteroarylene having 5 to 6 ring atoms, and combinations thereof;
A.sub.2 is, at each occurrence identically or differently, selected from the group consisting of: O, S, Se, NR″, SiR″R″, GeR″R″, BR″, PR″, P(O)R″, following groups unsubstituted or substituted by one or at least two R.sub.a2: alkylene having 1 to 20 carbon atoms, heteroalkylene having 1 to 20 carbon atoms, cycloalkylene having 3 to 20 carbon atoms, heterocyclene having 3 to 20 ring atoms, arylene having 6 to 30 carbon atoms and heteroarylene having 3 to 30 carbon atoms, and combinations thereof;
R′, R″, R.sub.x, 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 aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;
adjacent substituents R′, R″, R.sub.x, R.sub.a2, R.sub.a3 can be optionally joined to form a ring;
the length of A is at least 6.7 Å;
“*” represents a position where A is attached;
when A.sub.1 is selected from phenylene unsubstituted or substituted by one or at least two R.sub.a1 or heteroarylene having 5 to 6 ring atoms unsubstituted or substituted by one or at least two R.sub.a1, A.sub.2 and R.sub.a1 need to satisfy the following conditions:
1) A.sub.2 that is directly attached to A.sub.1 is, at each occurrence identically or differently, selected from the group consisting of: O, S, Se, NR″, SiR″R″, GeR″R″, BR″, PR″, P(O)R″, following groups unsubstituted or substituted by one or at least two R.sub.a2: alkylene having 1 to 20 carbon atoms, heteroalkylene having 1 to 20 carbon atoms, cycloalkylene having 3 to 20 carbon atoms and heterocyclene having 3 to 20 ring atoms, and combinations thereof; and
2) R.sub.a1 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 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.
[0094] Herein, the expression that “adjacent substituents R′, R″, R.sub.x, 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 two substituents R′, two substituents R″, two substituents R.sub.x, two substituents R.sub.a2, substituents R.sub.a2 and R.sub.a3, 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.
[0095] Herein, the “ring atoms” in the “heteroarylene having 5 to 6 ring atoms” refer to those atoms that are bonded to form a heterocyclic structure having aromaticity. The carbon atoms and heteroatoms (comprising, but not limited to, O, S, N, Se, Si, Ge, etc.) in the ring are all counted in the number of ring atoms. When the ring is substituted by a substituent, the atoms comprised in the substituent are excluded from the number of ring atoms. For example, the number of ring atoms of pyridyl, pyrimidine and triazine is 6; the number of ring atoms of pyrrolidine, thienyl, furyl, imidazolyl and triazolyl is 5. The various examples described herein are examples only, and so on in other cases.
[0096] Herein, the expression that “the length of A is at least 6.7 Å” is intended to mean that the distance between the atom in Formula 2 that is directly attached to Formula 1 and the atom in Formula 2 that is furthest from the atom in Formula 2 that is directly attached to Formula 1 is the length of A, and the length is at least 6.7 Å. In the present application, the length of A is calculated by ChemBio3D Ultra 14.0.0.117, optimized by MM2. For example, when A is 4-trimethylsilylphenyl, that is, Formula 2 is
##STR00017##
the longest distance is the distance between the “C” that is directly attached to Formula 1 and the farthest hydrogen atom (as indicated by the dashed arrow), and the length of the substituent obtained by the calculation method of the present application is 6.6 Å, that is, the group A mentioned in the present application does not contain this structure. In another example, when A is 4-propylphenyl, that is, Formula 2 is
##STR00018##
the longest distance is the distance between the “C” that is directly attached to Formula 1 and the farthest hydrogen atom (as indicated by the dashed arrow), and the length of the substituent obtained by the calculation method of the present application is 7.3 Å, that is, the group A mentioned in the present application contains this structure, to which the other cases are similar.
[0097] Herein, “A.sub.2 that is directly attached to A.sub.1” refers to the A.sub.2 that is directly bonded to A.sub.1 through a chemical bond. For example, when a is 1, that is, Formula 2 has the following structure: *-A.sub.1—A.sub.2—R.sub.a3, at this point, there is only one A.sub.z, and this A.sub.2 is directly bonded to A.sub.1; in another example, when a is 2, that is, Formula 2 has the following structure: *-A.sub.1—A.sub.2—A.sub.2—R.sub.a3, at this point, there are two A.sub.2 in Formula 2, and the first A.sub.2 from the left is the A.sub.2 directly attached to A.sub.1; and so on when a is 3, 4 or 5.
[0098] According to an embodiment of the present disclosure, a metal complex is disclosed. The metal complex comprises a metal M and a ligand L.sub.a coordinated to the metal M, wherein the metal M is selected from metals having a relative atomic mass greater than 40, and L.sub.a has a structure represented by Formula 1:
##STR00019##
wherein in Formula 1,
[0099] 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 combinations thereof;
[0100] X is selected from the group consisting of O, S, Se, NR′, CR′R′, SiR′R′, and GeR′R′; when two R′ are present, the two R′ are identical or different;
[0101] X.sub.1 to X.sub.7 are, at each occurrence identically or differently, selected from C, CR.sub.x or N; at least one of X.sub.1 to X.sub.4 is C and is attached to Cy;
[0102] X.sub.1, X.sub.2, X.sub.3 or X.sub.4 is attached to the metal M through a metal-carbon bond or a metal-nitrogen bond;
[0103] at least one of X.sub.1 to X.sub.7 is CR.sub.x, wherein the R.sub.x is cyano or fluorine;
[0104] R′ and R.sub.x are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;
[0105] A has a structure represented by Formula 2:
##STR00020##
[0106] wherein a is selected from 1, 2, 3, 4 or 5;
[0107] the length of A is at least 6.7 Å;
[0108] “” represents a position where A is attached;
[0109] A.sub.1, A.sub.2, and R.sub.a3 need to satisfy at least one of the following two cases:
[0110] the first case is as follows: A.sub.1 is, at each occurrence identically or differently, selected from the group consisting of: O, S, Se, NR″, SiR″R″, GeR″R″, BR″, PR″, P(O)R″, following groups unsubstituted or substituted by one or at least two R.sub.a1: alkylene having 1 to 20 carbon atoms, heteroalkylene having 1 to 20 carbon atoms, cycloalkylene having 3 to 20 carbon atoms and heterocyclene having 3 to 20 ring atoms, and combinations thereof;
[0111] A.sub.2 is, at each occurrence identically or differently, selected from the group consisting of: O, S, Se, NR″, SiR″R″, GeR″R″, BR″, PR″, P(O)R″, alkylene having 1 to 20 carbon atoms unsubstituted or substituted by one or at least two R.sub.a2, heteroalkylene having 1 to 20 carbon atoms unsubstituted or substituted by one or at least two R.sub.a2, cycloalkylene having 3 to 20 carbon atoms unsubstituted or substituted by one or at least two R.sub.a2, heterocyclene having 3 to 20 ring atoms unsubstituted or substituted by one or at least two R.sub.a2, arylene having 6 to 30 carbon atoms unsubstituted or substituted by one or at least two R.sub.a2, heteroarylene having 3 to 30 carbon atoms unsubstituted or substituted by one or at least two R.sub.a2, and combinations thereof;
[0112] R″, 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 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″, R.sub.x, R.sub.a2, R.sub.a3 can be optionally joined to form a ring;
[0113] the second case is as follows: A.sub.1 is, at each occurrence identically or differently, selected from phenylene unsubstituted or substituted by one or at least two R.sub.a1, heteroarylene having 5 to 6 ring atoms unsubstituted or substituted by one or at least two R.sub.a1 or combinations thereof;
[0114] A.sub.2 is, at each occurrence identically or differently, selected from the group consisting of: O, S, Se, NR″, SiR″R″, GeR″R″, BR″, PR″, P(O)R″, following groups unsubstituted or substituted by one or at least two R.sub.a2: alkylene having 1 to 20 carbon atoms, heteroalkylene having 1 to 20 carbon atoms, cycloalkylene having 3 to 20 carbon atoms and heterocyclene having 3 to 20 ring atoms, and combinations thereof;
[0115] R″, 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 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
[0116] R.sub.a1 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 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;
[0117] adjacent substituents R′, R″, R.sub.x, R.sub.a2, R.sub.a1 can be optionally joined to form a ring.
[0118] According to an embodiment of the present disclosure, the length of A is greater than or equal to 6.7 Å and less than or equal to 22 Å.
[0119] According to an embodiment of the present disclosure, the length of A is greater than or equal to 6.7 Å and less than 13.3 Å.
[0120] According to an embodiment of the present disclosure, the length of A is greater than or equal to 7.0 Å and less than 13.3 Å.
[0121] According to an embodiment of the present disclosure, the length of A is greater than or equal to 7.0 Å and less than or equal to 10.5 Å.
[0122] According to an embodiment of the present disclosure, A.sub.1 is, at each occurrence identically or differently, selected from phenylene unsubstituted or substituted by one or at least two R.sub.a1 or heteroarylene having 5 to 6 ring atoms unsubstituted or substituted by one or at least two R.sub.a1; A.sub.2 is, at each occurrence identically or differently, selected from the group consisting of: O, S, NR″, SiR″R″, GeR″R″, following groups unsubstituted or substituted by one or at least two R.sub.a2: alkylene having 1 to 6 carbon atoms, cycloalkylene having 3 to 20 ring carbon atoms and heterocyclene having 3 to 20 ring atoms, and combinations thereof.
[0123] According to an embodiment of the present disclosure, A.sub.1 is, at each occurrence identically or differently, selected from phenylene unsubstituted or substituted by one or at least two R.sub.a1 or heteroarylene having 6 ring atoms unsubstituted or substituted by one or at least two R.sub.a1; A.sub.2 is, at each occurrence identically or differently, selected from cycloalkylene having 3 to 20 ring carbon atoms unsubstituted or substituted by one or at least two R.sub.a2, heterocyclene having 3 to 20 ring atoms unsubstituted or substituted by one or at least two R.sub.a2 or combinations thereof.
[0124] According to an embodiment of the present disclosure, A.sub.1 is, at each occurrence identically or differently, selected from phenylene unsubstituted or substituted by one or at least two R.sub.a1; A.sub.2 is, at each occurrence identically or differently, selected from cycloalkylene having 5 to 12 ring carbon atoms unsubstituted or substituted by one or at least two R.sub.a2, heterocyclene unsubstituted or substituted by one or at least two R.sub.a2 and having 5 to 12 ring atoms or combinations thereof.
[0125] According to an embodiment of the present disclosure, A.sub.1 is, at each occurrence identically or differently, selected from the group consisting of: O, S, NR″, SiR″R″, GeR″R″, following groups unsubstituted or substituted by one or at least two R.sub.a1: alkylene having 1 to 20 carbon atoms, heteroalkylene having 1 to 20 carbon atoms, cycloalkylene having 3 to 20 carbon atoms and heterocyclene having 3 to 20 ring atoms, and combinations thereof; A.sub.2 is, at each occurrence identically or differently, selected from following groups unsubstituted or substituted by one or at least two R.sub.a2: alkylene having 1 to 20 carbon atoms, heteroalkylene having 1 to 20 carbon atoms, cycloalkylene having 3 to 20 carbon atoms, heterocyclene having 3 to 20 ring atoms, arylene having 6 to 30 carbon atoms, heteroarylene having 3 to 30 carbon atoms, and combinations thereof.
[0126] According to an embodiment of the present disclosure, A.sub.1 is, at each occurrence identically or differently, selected from the group consisting of: O, S, NR″, SiR″R″, GeR″R″, following groups unsubstituted or substituted by one or at least two R.sub.a1: cycloalkylene having 3 to 10 carbon atoms and heterocyclene having 3 to 10 ring atoms, and combinations thereof; A.sub.2 is, at each occurrence identically or differently, selected from following groups unsubstituted or substituted by one or at least two R.sub.a2: cycloalkylene having 3 to 10 carbon atoms, heterocyclene having 3 to 10 ring atoms, arylene having 6 to 18 carbon atoms and heteroarylene having 3 to 18 ring atoms, and combinations thereof.
[0127] According to an embodiment of the present disclosure, Cy is selected from the group consisting of the following structures:
##STR00021##
[0128] wherein,
[0129] R represents, at each occurrence identically or differently, mono-substitution, multiple substitutions or no substitution; when a plurality of R are present, the plurality of R are identical or different;
[0130] 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;
[0131] two adjacent substituents R can be optionally joined to form a ring;
[0132] “#” represents a position where the metal M is attached, and
##STR00022##
represents a position where X.sub.1, X.sub.2, X.sub.3 or X.sub.4 is attached.
[0133] Herein, the expression that “two adjacent substituents R can be optionally joined to form a ring” is intended to mean that any one or more of substituent groups consisting 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.
[0134] According to an embodiment of the present disclosure, L.sub.a is, at each occurrence identically or differently, selected from the group consisting of:
##STR00023## ##STR00024## ##STR00025## ##STR00026## ##STR00027## ##STR00028##
[0135] wherein,
[0136] X is selected from the group consisting of O, S, Se, NR′, CR′R′, SiR′R′, and GeR′R′; when two R′ are present, the two R′ are identical or different;
[0137] R and R.sub.x represent, at each occurrence identically or differently, mono-substitution, multiple substitutions or no substitution;
[0138] at least one of R.sub.x is fluorine or cyano;
[0139] A has a structure represented by Formula 2:
##STR00029##
[0140] wherein a is selected from 1, 2, 3, 4 or 5;
[0141] A.sub.1 is, at each occurrence identically or differently, selected from the group consisting of: O, S, Se, NR″, SiR″R″, GeR″R″, BR″, PR″, P(O)R″, following groups unsubstituted or substituted by one or at least two R.sub.a1: alkylene having 1 to 20 carbon atoms, heteroalkylene having 1 to 20 carbon atoms, cycloalkylene having 3 to 20 carbon atoms, heterocyclene having 3 to 20 ring atoms, phenylene and heteroarylene having 5 to 6 ring atoms, and combinations thereof;
[0142] A.sub.2 is, at each occurrence identically or differently, selected from the group consisting of: O, S, Se, NR″, SiR″R″, GeR″R″, BR″, PR″, P(O)R″, following groups unsubstituted or substituted by one or at least two R.sub.a2: alkylene having 1 to 20 carbon atoms, heteroalkylene having 1 to 20 carbon atoms, cycloalkylene having 3 to 20 carbon atoms, heterocyclene having 3 to 20 ring atoms, arylene having 6 to 30 carbon atoms and heteroarylene having 3 to 30 carbon atoms, and combinations thereof;
[0143] R, R′, R″, R.sub.x, 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 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;
[0144] adjacent substituents R, R″, R.sub.x, R.sub.a2, R.sub.a3 can be optionally joined to form a ring;
[0145] “*” represents a position where A is attached;
[0146] when A.sub.1 is selected from phenylene unsubstituted or substituted by one or at least two R.sub.a1 or heteroarylene having 5 to 6 ring atoms unsubstituted or substituted by one or at least two R.sub.a1, A.sub.2 and R.sub.a1 need to satisfy the following conditions:
[0147] 1) A.sub.2 that is directly attached to A.sub.1 is, at each occurrence identically or differently, selected from the group consisting of: O, S, Se, NR″, SiR″R″, GeR″R″, BR″, PR″, P(O)R″, alkylene having 1 to 20 carbon atoms unsubstituted or substituted by one or at least two R.sub.a2, heteroalkylene having 1 to 20 carbon atoms unsubstituted or substituted by one or at least two R.sub.a2, cycloalkylene having 3 to 20 carbon atoms unsubstituted or substituted by one or at least two R.sub.a2, heterocyclene having 3 to 20 ring atoms unsubstituted or substituted by one or at least two R.sub.a2, and combinations thereof; and
[0148] 2) R.sub.a1 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 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.
[0149] Herein, the expression that “adjacent substituents R, R′, R″, R.sub.x, 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 two substituents R, two substituents two substituents R″, two substituents R.sub.x, two substituents R.sub.a2, substituents R.sub.a2 and R.sub.a3, 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.
[0150] According to an embodiment of the present disclosure, the metal complex has a general formula of M(L.sub.a).sub.m(L.sub.b).sub.n(L.sub.c).sub.q;
[0151] wherein,
[0152] M is, at each occurrence identically or differently, selected from the group consisting of Cu, Ag, Au, Ru, Rh, Pd, Os, Ir, and Pt;
[0153] L.sub.a, L.sub.b, and L.sub.c are a first ligand, a second ligand and a third ligand coordinated to the metal M, respectively, and L.sub.c is identical to or different from L.sub.a or L.sub.b; wherein L.sub.a, L.sub.b, and L.sub.c can be optionally joined to form a multidentate ligand; for example, any two of L.sub.a, L.sub.b, and L.sub.c can be joined to form a tetradentate ligand; in another example, L.sub.a, L.sub.b, and L.sub.c can be joined to each other to form a hexadentate ligand; in another example, none of L.sub.a, L.sub.b, and L.sub.c are joined so that no multidentate ligand is formed;
[0154] m is selected from 1, 2 or 3, n is selected from 0, 1 or 2, q is selected from 0, 1 or 2, and m+n+q equals an oxidation state of the metal M; when m is greater than or equal to 2, a plurality of L.sub.a are identical or different; when n is equal to 2, two L.sub.b are identical or different; when q is equal to 2, two L.sub.c are identical or different;
[0155] L.sub.b and L.sub.c are, at each occurrence identically or differently, selected from the group consisting of the following structures:
##STR00030##
[0156] wherein,
[0157] R.sub.a and R.sub.b represent, at each occurrence identically or differently, mono-substitution, multiple substitutions or no substitution;
[0158] 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;
[0159] 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;
[0160] 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.
[0161] Herein, the expression that “adjacent substituents R.sub.a, R.sub.b, R.sub.c, R.sub.N1, R.sub.C1, and R.sub.C2 can be optionally joined to form a ring” is intended to mean that any one or more of groups of adjacent substituents, such as two substituents R.sub.a, two substituents R.sub.b, substituents R.sub.a and R.sub.b, substituents R.sub.a and R.sub.c, substituents R.sub.b and R.sub.c, substituents R.sub.a and R.sub.N1, substituents R.sub.b and R.sub.N1, substituents R.sub.a and R.sub.C1, substituents R.sub.a and R.sub.C2, substituents R.sub.b and R.sub.C1, substituents R.sub.b and R.sub.C2, and substituents R.sub.C1 and R.sub.C2, can be joined to form a ring. Obviously, it is possible that none of these substituents are joined to form a ring.
[0162] 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.
[0163] According to an embodiment of the present disclosure, the metal M is, at each occurrence identically or differently, selected from Pt or Ir.
[0164] According to an embodiment of the present disclosure, the metal complex Ir(L.sub.a).sub.m(L.sub.b).sub.3-m has a structure represented by Formula 3:
##STR00031##
[0165] wherein,
[0166] m is selected from 1, 2 or 3; when m is selected from 1, two L.sub.b are identical or different;
[0167] when m is selected from 2 or 3, a plurality of L.sub.a are identical or different;
[0168] Y.sub.1 to Y.sub.4 are, at each occurrence identically or differently, selected from CR.sub.y or N;
[0169] X is selected from the group consisting of O, S, Se, NR′, CR′R′, SiR′R′, and GeR′R′; when two R′ are present, the two R′ are identical or different;
[0170] X.sub.3 to X.sub.7 are, at each occurrence identically or differently, selected from CR.sub.x or N;
[0171] at least one of X.sub.3 to X.sub.7 is CR.sub.x, wherein the R.sub.x is cyano or fluorine;
[0172] A has a structure represented by Formula 2:
##STR00032##
[0173] wherein a is selected from 1, 2, 3, 4 or 5;
[0174] A.sub.1 is, at each occurrence identically or differently, selected from the group consisting of: O, S, Se, NR″, SiR″R″, GeR″R″, BR″, PR″, P(O)R″, following groups unsubstituted or substituted by one or at least two R.sub.a1: alkylene having 1 to 20 carbon atoms, heteroalkylene having 1 to 20 carbon atoms, cycloalkylene having 3 to 20 carbon atoms, heterocyclene having 3 to 20 ring atoms, phenylene and heteroarylene having 5 to 6 ring atoms, and combinations thereof;
[0175] A.sub.2 is, at each occurrence identically or differently, selected from the group consisting of: O, S, Se, NR″, SiR″R″, GeR″R″, BR″, PR″, P(O)R″, following groups unsubstituted or substituted by one or at least two R.sub.a2: alkylene having 1 to 20 carbon atoms, heteroalkylene having 1 to 20 carbon atoms, cycloalkylene having 3 to 20 carbon atoms, heterocyclene having 3 to 20 ring atoms, arylene having 6 to 30 carbon atoms and heteroarylene having 3 to 30 carbon atoms, and combinations thereof;
[0176] R′, R″, R.sub.x, R.sub.y, R.sub.a1, R.sub.a2, R.sub.a3, and R.sub.1 to R.sub.8 are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted 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;
[0177] adjacent substituents R.sub.1 to R.sub.8 can be optionally joined to form a ring;
[0178] adjacent substituents R′, R″, R.sub.x, R.sub.y, R.sub.a2, R.sub.a31 can be optionally joined to form a ring;
[0179] the length of A is at least 6.7 Å;
[0180] “” represents a position where A is attached;
[0181] when A.sub.1 is, at each occurrence identically or differently, selected from phenylene unsubstituted or substituted by one or at least two R.sub.a1 or heteroarylene having 5 to 6 ring atoms unsubstituted or substituted by one or at least two R.sub.a1, A.sub.2 and R.sub.a1 need to satisfy the following conditions:
[0182] 1) A.sub.2 that is directly attached to A.sub.1 is, at each occurrence identically or differently, selected from the group consisting of: O, S, Se, NR″, SiR″R″, GeR″R″, BR″, PR″, P(O)R″, alkylene having 1 to 20 carbon atoms unsubstituted or substituted by one or at least two R.sub.a2, heteroalkylene having 1 to 20 carbon atoms unsubstituted or substituted by one or at least two R.sub.a2, cycloalkylene having 3 to 20 carbon atoms unsubstituted or substituted by one or at least two R.sub.a2, heterocyclene having 3 to 20 ring atoms unsubstituted or substituted by one or at least two R.sub.a2, and combinations thereof; and
[0183] 2) R.sub.a1 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 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.
[0184] Herein, the expression that “adjacent substituents R′, R″, R.sub.x, R.sub.y, R.sub.a2, R.sub.a3 can be optionally joined to form a ring” is intended to mean that any one or at least two of groups of adjacent substituents, such as two substituents R′, two substituents R″, two substituents R.sub.x, two substituents R.sub.y, two substituents R.sub.a2, two substituents R.sub.a3, substituents R′ and R.sub.x, 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.
[0185] The expression that “adjacent substituents R.sub.1 to R.sub.8 can be optionally joined to form a ring” is intended to mean that any one or at least two of groups of adjacent substituents, such as adjacent substituents R.sub.1 and R.sub.2, adjacent substituents R.sub.2 and R.sub.3, adjacent substituents R.sub.3 and R.sub.4, adjacent substituents R.sub.5 and R.sub.4, adjacent substituents R.sub.5 and R.sub.6, adjacent substituents R.sub.7 and R.sub.6, and adjacent substituents R.sub.7 and R.sub.8, can be joined to form a ring. Obviously, it is possible that none of these substituents are joined to form a ring.
[0186] According to an embodiment of the present disclosure, the metal complex Ir(L.sub.a).sub.m(L.sub.b).sub.3-m has a structure represented by Formula 3A:
##STR00033##
[0187] wherein,
[0188] m is selected from 1, 2 or 3; when m is selected from 1, two L.sub.b are identical or different; when m is selected from 2 or 3, a plurality of L.sub.a are identical or different;
[0189] X is selected from the group consisting of O, S, Se, NR′, CR′R′, SiR′R′, and GeR′R′; when two R′ are present, the two R′ are identical or different;
[0190] R.sub.x and R.sub.y represent, at each occurrence identically or differently, mono-substitution, multiple substitutions or no substitution;
[0191] at least one R.sub.x is cyano or fluorine; and
[0192] A has a structure represented by Formula 2:
##STR00034##
[0193] wherein a is selected from 1, 2, 3, 4 or 5;
[0194] A.sub.1 is, at each occurrence identically or differently, selected from the group consisting of: O, S, Se, NR″, SiR″R″, GeR″R″, BR″, PR″, P(O)R″, following groups unsubstituted or substituted by one or at least two R.sub.a1: alkylene having 1 to 20 carbon atoms, heteroalkylene having 1 to 20 carbon atoms, cycloalkylene having 3 to 20 carbon atoms, heterocyclene having 3 to 20 ring atoms, phenylene and heteroarylene having 5 to 6 ring atoms, and combinations thereof;
[0195] A.sub.2 is, at each occurrence identically or differently, selected from the group consisting of: O, S, Se, NR″, SiR″R″, GeR″R″, BR″, PR″, P(O)R″, following groups unsubstituted or substituted by one or at least two R.sub.a2: alkylene having 1 to 20 carbon atoms, heteroalkylene having 1 to 20 carbon atoms, cycloalkylene having 3 to 20 carbon atoms, heterocyclene having 3 to 20 ring atoms, arylene having 6 to 30 carbon atoms and heteroarylene having 3 to 30 carbon atoms, and combinations thereof;
[0196] R′, R″, R.sub.x, R.sub.y, R.sub.a1, R.sub.a2, R.sub.a3, and R.sub.1 to R.sub.8 are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted 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;
[0197] adjacent substituents R.sub.1 to R.sub.8 can be optionally joined to form a ring;
[0198] adjacent substituents R′, R″, R.sub.x, R.sub.y, R.sub.a2, R.sub.a31 can be optionally joined to form a ring;
[0199] the length of A is at least 6.7 Å;
[0200] “” represents a position where A is attached;
[0201] when A.sub.1 is, at each occurrence identically or differently, selected from phenylene unsubstituted or substituted by one or at least two R.sub.a1 or heteroarylene having 5 to 6 ring atoms unsubstituted or substituted by one or at least two R.sub.a1, A.sub.2 and R.sub.a1 need to satisfy the following conditions:
[0202] 1) A.sub.2 that is directly attached to A.sub.1 is, at each occurrence identically or differently, selected from the group consisting of: O, S, Se, NR″, SiR″R″, GeR″R″, BR″, PR″, P(O)R″, alkylene having 1 to 20 carbon atoms unsubstituted or substituted by one or at least two R.sub.a2, heteroalkylene having 1 to 20 carbon atoms unsubstituted or substituted by one or at least two R.sub.a2, cycloalkylene having 3 to 20 carbon atoms unsubstituted or substituted by one or at least two R.sub.a2, heterocyclene having 3 to 20 ring atoms unsubstituted or substituted by one or at least two R.sub.a2, and combinations thereof; and [0203] 2) R.sub.a1 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 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.
[0204] According to an embodiment of the present disclosure, X is selected from O or S.
[0205] According to an embodiment of the present disclosure, X is O.
[0206] According to an embodiment of the present disclosure, X.sub.1 to X.sub.7 are, at each occurrence identically or differently, selected from C or CR.sub.x.
[0207] According to an embodiment of the present disclosure, at least one of X.sub.1 to X.sub.7 is N, for example, one of X.sub.1 to X.sub.7 is N or two of X.sub.1 to X.sub.7 are N.
[0208] According to an embodiment of the present disclosure, in Formula 3, X.sub.3 to X.sub.7 are, at each occurrence identically or differently, selected from CR.sub.x.
[0209] According to an embodiment of the present disclosure, in Formula 3, at least one of X.sub.3 to X.sub.7 is N, for example, one of X.sub.3 to X.sub.7 is N or two of X.sub.3 to X.sub.7 are N.
[0210] According to an embodiment of the present disclosure, Y.sub.1 to Y.sub.4 are, at each occurrence identically or differently, selected from CR.sub.Y.
[0211] According to an embodiment of the present disclosure, at least one of Y.sub.1 to Y.sub.4 is N, for example, one of Y.sub.1 to Y.sub.4 is N or two of Y.sub.1 to Y.sub.4 are N.
[0212] According to an embodiment of the present disclosure, a is selected from 1, 2 or 3.
[0213] According to an embodiment of the present disclosure, a is selected from 1.
[0214] According to an embodiment of the present disclosure, at least one of X.sub.3 to X.sub.7 is selected from CR.sub.x, wherein the R.sub.x is a cyano group or fluorine.
[0215] According to an embodiment of the present disclosure, at least one of X.sub.5 to X.sub.7 is selected from CR.sub.x, wherein the R.sub.x is cyano or fluorine.
[0216] According to an embodiment of the present disclosure, X.sub.7 is CR.sub.x, wherein the R.sub.x is cyano or fluorine.
[0217] According to an embodiment of the present disclosure, X.sub.7 is CR.sub.x wherein the R.sub.x is cyano.
[0218] According to an embodiment of the present disclosure, at least one of X.sub.3 to X.sub.7 is CR.sub.x, wherein the R.sub.x is cyano or fluorine; remaining R.sub.x 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, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, a cyano group, and combinations thereof.
[0219] According to an embodiment of the present disclosure, at least one of X.sub.5 to X.sub.7 is CR.sub.x, wherein the R.sub.x is cyano or fluorine; remaining R.sub.x are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, fluorine, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms, substituted or unsubstituted aryl having 6 to 12 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 12 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 6 carbon atoms, a cyano group, and combinations thereof.
[0220] According to an embodiment of the present disclosure, X.sub.7 is CR.sub.x, wherein the R.sub.x is cyano or fluorine; remaining R.sub.x are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms, and combinations thereof.
[0221] According to an embodiment of the present disclosure, R.sub.a1 is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 4 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, a hydroxyl group, a sulfanyl group, and combinations thereof.
[0222] According to an embodiment of the present disclosure, R.sub.a1 is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, fluorine, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms, substituted or unsubstituted alkylsilyl having 4 to 15 carbon atoms, and combinations thereof.
[0223] According to an embodiment of the present disclosure, R.sub.a1 is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, fluorine, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, cyclopentyl, cyclohexyl, deuterated methyl, deuterated ethyl, deuterated propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated t-butyl, deuterated cyclopentyl, deuterated cyclohexyl, trimethylsilyl, and combinations thereof.
[0224] According to an embodiment of the present disclosure, 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 arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, a hydroxyl group, a sulfanyl group, and combinations thereof.
[0225] According to an embodiment of the present disclosure, R.sub.a2 and R.sub.a3 are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, fluorine, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms, substituted or unsubstituted aryl having 6 to 18 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 18 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 15 carbon atoms, and combinations thereof.
[0226] According to an embodiment of the present disclosure, R.sub.a2 and R.sub.a3 are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, fluorine, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, cyclopentyl, cyclohexyl, deuterated methyl, deuterated ethyl, deuterated propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated t-butyl, deuterated cyclopentyl, deuterated cyclohexyl, phenyl, pyridyl, trimethylsilyl, and combinations thereof.
[0227] According to an embodiment of the present disclosure, A is, at each occurrence identically or differently, selected from the group consisting of A-1 to A-179, wherein for the specific structures of A-1 to A-179, reference is made to claim 13; optionally, hydrogen in A-1 to A-179 can be partially or fully substituted with deuterium, wherein “” represents a position where A is attached.
[0228] Herein, the length of A is calculated by ChemBio3D Ultra 14.0.0.117, optimized by MM2. Structures and lengths of some substituents are illustrated in the following table.
TABLE-US-00001 Length L Structure (Å)
[0229] According to an embodiment of the present disclosure, in Formula 3, R.sub.y is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, and combinations thereof.
[0230] According to an embodiment of the present disclosure, in Formula 3, 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 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms, substituted or unsubstituted aryl having 6 to 12 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 11 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 6 carbon atoms, a cyano group, and combinations thereof.
[0231] According to an embodiment of the present disclosure, in Formula 3, R.sub.y is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, cyclopentyl, cyclohexyl, deuterated methyl, deuterated ethyl, deuterated propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated t-butyl, deuterated cyclopentyl, deuterated cyclohexyl, phenyl, pyridyl, trimethylsilyl, and combinations thereof.
[0232] According to an embodiment of the present disclosure, in Formula 3, at least one R.sub.y is selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, and combinations thereof.
[0233] According to an embodiment of the present disclosure, in Formula 3, at least one or at least two of R.sub.5 to R.sub.8 is(are), at each occurrence identically or differently, selected from substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms or combinations thereof, and the total number of carbon atoms in R.sub.5 to R.sub.8 is at least 4.
[0234] According to an embodiment of the present disclosure, in Formula 3, at least one or at least two of R.sub.6 and R.sub.7 is(are) selected from substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms or combinations thereof, and the total number of carbon atoms in R.sub.6 and R.sub.7 is at least 4.
[0235] According to an embodiment of the present disclosure, in Formula 3, R.sub.7 is selected from substituted or unsubstituted alkyl having 4 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 4 to 20 ring carbon atoms or combinations thereof.
[0236] According to an embodiment of the present disclosure, in Formula 3, at least one or at least two or at least three or all of R.sub.2, R.sub.3, R.sub.6, and R.sub.7 is(are) selected from the group consisting of: deuterium, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, and combinations thereof.
[0237] According to an embodiment of the present disclosure, in Formula 3, at least one or at least two or at least three or all of R.sub.2, R.sub.3, R.sub.6, and R.sub.7 is (are) selected from the group consisting of: deuterium, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, and combinations thereof.
[0238] According to an embodiment of the present disclosure, in Formula 3, at least one or at least two or at least three or all of R.sub.2, R.sub.3, R.sub.6, and R.sub.7 is (are) selected from the group consisting of: deuterium, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, cyclopentyl, cyclohexyl, and combinations thereof; optionally, hydrogen in the above groups can be partially or fully substituted with deuterium.
[0239] According to an embodiment of the present disclosure, R″ is, at each occurrence identically or differently, selected from substituted or unsubstituted alkyl having 1 to 20 carbon atoms, 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 or combinations thereof.
[0240] According to an embodiment of the present disclosure, R″ is, at each occurrence identically or differently, selected from hydrogen, deuterium, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, cyclopentyl, cyclohexyl, deuterated methyl, deuterated ethyl, deuterated propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated t-butyl, deuterated cyclopentyl, deuterated cyclohexyl, phenyl, pyridyl or combinations thereof.
[0241] According to an embodiment of the present disclosure, R′ is selected from substituted or unsubstituted alkyl having 1 to 20 carbon atoms or substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms.
[0242] According to an embodiment of the present disclosure, R′ is selected from methyl or deuterated methyl.
[0243] 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 to L.sub.a938, wherein for the specific structures of L.sub.a1 to L.sub.a938, reference is made to claim 17.
[0244] According to an embodiment of the present disclosure, L.sub.b is, at each occurrence identically or differently, selected from the group consisting of L.sub.b1 to L.sub.b328, and for the specific structures of L.sub.b1 to L.sub.b328, reference is made to claim 18.
[0245] 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, and for the specific structures of L.sub.c1 to L.sub.c360, reference is made to claim 19.
[0246] According to an embodiment of the present disclosure, the metal complex has a structure of Ir(L.sub.a).sub.2(L.sub.b), wherein L.sub.a is, at each occurrence identically or differently, selected from any one or any two of the group consisting of L.sub.a1 to L.sub.a938, and L.sub.b is selected from any one of the group consisting of L.sub.b1 to L.sub.b328, wherein for the specific structures of L.sub.a1 to L.sub.a938, reference is made to claim 17, and for the specific structures of L.sub.b1 to L.sub.b328, reference is made to claim 18.
[0247] According to an embodiment of the present disclosure, the metal complex has a structure of Ir(L.sub.a)(L.sub.b).sub.2, wherein L.sub.a is, at each occurrence identically or differently, selected from any one of the group consisting of L.sub.a1 to L.sub.a938, and L.sub.b is selected from any one or any two of the group consisting of L.sub.b1 to L.sub.b328, wherein for the specific structures of L.sub.a1 to L.sub.a938, reference is made to claim 17, and for the specific structures of L.sub.b1 to L.sub.b328, reference is made to claim 18.
[0248] According to one embodiment of the present disclosure, the metal complex has a structure of Ir(L.sub.a).sub.3, wherein L.sub.a is, at each occurrence identically or differently, selected from any one or any two or any three of the group consisting of L.sub.a1 to L.sub.a938, wherein for the specific structures of L.sub.a1 to L.sub.a938, reference is made to claim 17.
[0249] According to an embodiment of the present disclosure, the metal complex has a structure of Ir(L.sub.a).sub.2(L.sub.c), wherein L.sub.a is, at each occurrence identically or differently, selected from any one or any two of the group consisting of L.sub.a1 to L.sub.a938, and L.sub.c is selected from any one of the group consisting of L.sub.c1 to L.sub.c360, wherein for the specific structures of L.sub.a1 to L.sub.a938, reference is made to claim 17, and for the specific structures of L.sub.c1 to L.sub.c360, reference is made to claim 19.
[0250] According to an embodiment of the present disclosure, the metal complex has a structure of Ir(L.sub.a)(L.sub.c).sub.2, wherein L.sub.a is, at each occurrence identically or differently, selected from any one of the group consisting of L.sub.a1 to L.sub.a938, and L.sub.c is selected from any one or any two of the group consisting of L.sub.c1 to L.sub.c360, wherein for the specific structures of L.sub.a1 to L.sub.a938, reference is made to claim 17, and for the specific structures of L.sub.c1 to L.sub.c360, reference is made to claim 19.
[0251] According to an embodiment of the present disclosure, the metal complex has a structure of Ir(L.sub.a)(L.sub.b)(L.sub.c), wherein L.sub.a is, at each occurrence identically or differently, selected from any one of the group consisting of L.sub.a1 to L.sub.a938, L.sub.b is selected from any one of the group consisting of L.sub.b1.sup.to L.sub.b328, and L.sub.c is selected from any one of the group consisting of L.sub.c1 to L.sub.c360, wherein for the specific structures of L.sub.a1 to L.sub.a938, reference is made to claim 17, for the specific structures of L.sub.b1 to L.sub.b328, reference is made to claim 18, and for the specific structures of L.sub.c1 to L.sub.c360, reference is made to claim 19.
[0252] According to an embodiment of the present disclosure, the metal complex is selected from the group consisting of metal complex 1 to metal complex 1900, wherein for the specific structures of metal complex 1 to metal complex 1900, reference is made to claim 20.
[0253] According to an embodiment of the present disclosure, the metal complex is selected from the group consisting of metal complex 1 to metal complex 1902, wherein for the specific structures of metal complex 1 to metal complex 1902, reference is made to claim 20.
[0254] According to an embodiment of the present disclosure, an electroluminescent device is disclosed. The electroluminescent device includes:
[0255] an anode,
[0256] a cathode, and
[0257] an organic layer disposed between the anode and the cathode, wherein the organic layer comprises the metal complex described in any one of the above-mentioned embodiments.
[0258] According to an embodiment of the present disclosure, the organic layer comprising the metal complex in the electroluminescent device is an emissive layer.
[0259] According to an embodiment of the present disclosure, the electroluminescent device emits green light.
[0260] According to an embodiment of the present disclosure, the electroluminescent device emits white light.
[0261] According to an embodiment of the present disclosure, the emissive layer of the electroluminescent device comprises a first host compound.
[0262] According to an embodiment of the present disclosure, the emissive layer of the electroluminescent device comprises a first host compound and a second host compound.
[0263] According to an embodiment of the present disclosure, the first host compound and/or the second host compound in the electroluminescent device comprise 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.
[0264] According to an embodiment of the present disclosure, the first host compound has a structure represented by Formula 4:
##STR00062##
[0265] wherein,
[0266] E.sub.1 to E.sub.6 are, at each occurrence identically or differently, selected from C, CR.sub.c or N, at least two of E.sub.1 to E.sub.6 are N, and at least one of E.sub.1 to E.sub.6 is C and is attached to Formula A:
##STR00063##
[0267] wherein,
[0268] Q is, at each occurrence identically or differently, selected from the group consisting of O, S, Se, N, NR′″, CR′″R′″, SiR′″R′″, GeR′″R′″, and R′″C═CR′″; when two R′″ are present, the two R′″ can be identical or different;
[0269] p is 0 or 1; r is 0 or 1;
[0270] when Q is selected from N, p is 0, and r is 1;
[0271] when Q is selected from the group consisting of O, S, Se, NR′″, CR′″R′″, SiR′″R′″, GeR′″R′″, and R′″C═CR′″, p is 1, and r is 0;
[0272] L is, at each occurrence identically or differently, selected from a single bond, substituted or unsubstituted alkylene having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkylene having 3 to 20 carbon atoms, substituted or unsubstituted arylene having 6 to 20 carbon atoms, substituted or unsubstituted heteroarylene having 3 to 20 carbon atoms or combinations thereof;
[0273] Q.sub.1 to Q.sub.8 are, at each occurrence identically or differently, selected from C, CR.sub.q or N;
[0274] R.sub.c, R′″, and R.sub.q are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;
[0275] “*” represents a position where Formula A is attached to Formula 4;
[0276] adjacent substituents R.sub.e, R′″, R.sub.q can be optionally joined to form a ring.
[0277] Herein, the expression that “adjacent substituents R.sub.e, R′″, R.sub.q can be optionally joined to form a ring” is intended to mean that any one or at least two of groups of adjacent substituents, such as two substituents R.sub.e, two substituents R′″, two substituents R.sub.q, and substituents R′″ and R.sub.q, can be joined to form a ring. Obviously, it is possible that none of these substituents are joined to form a ring.
[0278] According to an embodiment of the present disclosure, Q is, at each occurrence identically or differently, selected from O, S, N or NR″.
[0279] According to an embodiment of the present disclosure, E.sub.1 to E.sub.6 are, at each occurrence identically or differently, selected from C, CR.sub.e or N; wherein three of E.sub.1 to E.sub.6 are N, and at least one of E.sub.1 to E.sub.6 is CR.sub.e where in R.sub.e is, at each occurrence identically or differently, selected from the group consisting of: substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, and combinations thereof.
[0280] According to an embodiment of the present disclosure, E.sub.1 to E.sub.6 are, at each occurrence identically or differently, selected from C, CR.sub.e or N, three of E.sub.1 to E.sub.6 are N, at least one of E.sub.1 to E.sub.6 are is CR.sub.e, and R.sub.e is, at each occurrence identically or differently, selected from the group consisting of: substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuryl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl, and combinations thereof.
[0281] According to an embodiment of the present disclosure, R.sub.e is, at each occurrence identically or differently, selected from the group consisting of: substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, and combinations thereof.
[0282] According to an embodiment of the present disclosure, R.sub.e is, at each occurrence identically or differently, selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuryl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl, or combinations thereof.
[0283] According to an embodiment of the present disclosure, at least one or at least two of Q.sub.1 to Q.sub.8 is(are) selected from CR.sub.q, wherein the R.sub.q is selected from substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 5 to 30 carbon atoms or combinations thereof.
[0284] According to an embodiment of the present disclosure, at least one or at least two of Q.sub.1 to Q.sub.8 is(are) selected from CR.sub.q, wherein the R.sub.q is selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted pyridyl or combinations thereof.
[0285] According to an embodiment of the present disclosure, R′″ 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.
[0286] According to an embodiment of the present disclosure, R′″ is, at each occurrence identically or differently, selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuryl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl or combinations thereof.
[0287] According to an embodiment of the present disclosure, L is, at each occurrence identically or differently, selected from a single bond, substituted or unsubstituted arylene having 6 to 20 carbon atoms, substituted or unsubstituted heteroarylene having 3 to 20 carbon atoms or combinations thereof.
[0288] According to an embodiment of the present disclosure, L is, at each occurrence identically or differently, selected from a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted carbazolylene, substituted or unsubstituted dibenzofuranylene, substituted or unsubstituted dibenzothiophenylene or substituted or unsubstituted fluorenylene.
[0289] According to an embodiment of the present disclosure, L is, at each occurrence identically or differently, selected from a single bond, substituted or unsubstituted phenylene or substituted or unsubstituted biphenylene.
[0290] According to an embodiment of the present disclosure, the first host compound is selected from the group consisting of H-1 to H-243, wherein for the specific structures of H-1 to H-243, reference is made to claim 27.
[0291] According to an embodiment of the present disclosure, the second host compound in the electroluminescent device has a structure represented by Formula 5:
##STR00064##
[0292] wherein,
[0293] 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;
[0294] 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;
[0295] U is, at each occurrence identically or differently, selected from C, CR.sub.u or N, and at least one of U is C and is attached to L.sub.x;
[0296] R.sub.v and R.sub.u are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;
[0297] Ar.sub.6 is, at each occurrence identically or differently, selected from substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms or combinations thereof;
[0298] adjacent substituents R.sub.v and R.sub.u can be optionally joined to form a ring.
[0299] Herein, the expression that “adjacent substituents R.sub.v and R.sub.u can be optionally joined to form a ring” is intended to mean that any one or more of groups of adjacent substituents, such as two substituents R.sub.v, two substituents R.sub.u, and substituents R.sub.v and R.sub.u, can be joined to form a ring. Obviously, it is possible that none of these substituents are joined to form a ring.
[0300] According to an embodiment of the present disclosure, the second host compound in the electroluminescent device has a structure represented by one of Formula 5-a to Formula 5-j:
##STR00065## ##STR00066##
[0301] wherein,
[0302] 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;
[0303] V is, at each occurrence identically or differently, selected from CR.sub.v or N;
[0304] U is, at each occurrence identically or differently, selected from CR.sub.u or N;
[0305] R.sub.v and R.sub.u are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;
[0306] Ar.sub.6 is, at each occurrence identically or differently, selected from substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms or combinations thereof;
[0307] adjacent substituents R.sub.v and R.sub.u can be optionally joined to form a ring.
[0308] According to an embodiment of the present disclosure, the second host compound is selected from the group consisting of X-1 to X-150, wherein for the specific structures of X-1 to X-150, reference is made to claim 29.
[0309] 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.
[0310] 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.
[0311] 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.
[0312] Combination with Other Materials
[0313] 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.
[0314] 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.
[0315] 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
[0316] The method for preparing a compound of the present disclosure is not limited herein. Typically, the following compounds are taken as examples without limitations, and synthesis routes and preparation methods thereof are described below.
Synthesis Example 1: Synthesis of Metal Complex 1701
[0317] Step 1:
##STR00067##
[0318] 5-t-butyl-2-phenylpyridine (13.2 g, 62.9 mmol), iridium trichloride trihydrate (5.5 g, 15.7 mmol), 300 mL of 2-ethoxyethanol and 100 mL of water were sequentially added into a dry 500 mL round-bottom flask, purged with nitrogen three times, and heated and stirred at 130° C. for 24 hours under nitrogen protection. The reaction product was cooled, filtered, washed three times with methanol and n-hexane separately, and suction-dried to give 9.7 g of intermediate 1 (with a yield of 97%).
[0319] Step 2:
##STR00068##
[0320] Intermediate 1 (9.7 g, 7.7 mmol), 250 mL of anhydrous dichloromethane, 10 mL of methanol and silver trifluoromethanesulfonate (4.3 g, 16.7 mmol) were sequentially added into a dry 500 mL round-bottom flask, purged with nitrogen three times, and stirred overnight at room temperature under nitrogen protection. The reaction product was filtered with Celite and washed twice with dichloromethane. The organic phases were collected and concentrated under reduced pressure to give 13.2 g of intermediate 2 as a yellow solid (with a yield of 93%).
[0321] Step 3:
##STR00069##
[0322] Intermediate 2 (3.5 g, 4.3 mmol), intermediate 3 (3.3 g, 7.8 mmol) and 125 mL of ethanol were sequentially added into a dry 500 mL round-bottom flask, purged with nitrogen three times, heated at 100° C. and reacted for 24 hours under nitrogen protection. After the reaction was cooled, the reaction product was filtered with Celite, washed twice with methanol and n-hexane separately. Yellow solids above the Celite were dissolved with dichloromethane. The organic phases were collected, concentrated under reduced pressure, and purified by column chromatography to give metal complex 1701 as a yellow solid (2.3 g with a yield of 52%). The product was confirmed as the target product with a molecular weight of 1033.4.
Synthesis Example 2: Synthesis of Metal Complex 105
[0323] Step 1:
##STR00070##
[0324] Intermediate 4 (1.0 mmol, 2.3 mmol), intermediate 2 (1.8 g, 2.3 mmol), 30 mL of 2-ethoxyethanol and 30 mL of N,N-dimethylformamide were sequentially added into a dry 250 mL round-bottom flask, purged with nitrogen three times, heated at 100° C. and reacted for 72 hours under nitrogen protection. After the reaction was cooled, the reaction product was filtered with Celite, washed twice with methanol and n-hexane separately. Yellow solids above the Celite were dissolved with dichloromethane. The organic phases were collected, concentrated under reduced pressure, and purified by column chromatography to give metal complex 105 as a yellow solid (0.6 g with a yield of 25%). The product was confirmed as the target product with a molecular weight of 1040.4.
Synthesis Example 3: Synthesis of Metal Complex 67
[0325] Step 1:
##STR00071##
[0326] Intermediate 5 (1.8 g, 4.3 mmol), intermediate 2 (2.7 g, 3.2 mmol), 50 mL of 2-ethoxyethanol and 50 mL of N,N-dimethylformamide were sequentially added into a dry 250 mL round-bottom flask, purged with nitrogen three times, heated at 100° C. and reacted for 96 hours under nitrogen protection. After the reaction was cooled, the reaction product was filtered with Celite, washed twice with methanol and n-hexane separately. Yellow solids above the Celite were dissolved with dichloromethane. The organic phases were collected, concentrated under reduced pressure, and purified by column chromatography to give metal complex 67 as a yellow solid (0.4 g with a yield of 12%). The product was confirmed as the target product with a molecular weight of 1026.4.
Synthesis Example 4: Synthesis of Metal Complex 257
[0327] Step 1:
##STR00072##
[0328] Intermediate 6 (1.3 g, 3.0 mmol), intermediate 2 (2.1 g, 2.5 mmol), 30 mL of 2-ethoxyethanol and 30 mL of N,N-dimethylformamide were sequentially added into a dry 250 mL round-bottom flask, purged with nitrogen three times, heated at 100° C. and reacted for 3 days under nitrogen protection. After the reaction was cooled, the reaction product was filtered with Celite, washed twice with methanol and n-hexane separately. Yellow solids above the Celite were dissolved with dichloromethane. The organic phases were collected, concentrated under reduced pressure, and purified by column chromatography to give metal complex 257 as a yellow solid (0.3 g with a yield of 11%). The product was confirmed as the target product with a molecular weight of 1042.4.
Synthesis Example 5: Synthesis of Metal Complex 1901
[0329] Step 1:
##STR00073##
[0330] Intermediate 7 (0.6 g, 1.2 mmol), intermediate 8 (0.9 g, 1.2 mmol), 15 mL of 2-ethoxyethanol and 15 mL of N,N-dimethylformamide were sequentially added into a dry 250 mL round-bottom flask, purged with nitrogen three times, heated at 100° C. and reacted for 5 days under nitrogen protection. After the reaction was cooled, the reaction product was filtered with Celite, washed twice with methanol and n-hexane separately. Yellow solids above the Celite were dissolved with dichloromethane. The organic phases were collected, concentrated under reduced pressure, and purified by column chromatography to give metal complex 1901 as a yellow solid (0.2 g with a yield of 17%). The product was confirmed as the target product with a molecular weight of 992.2.
[0331] The persons skilled in the art will appreciate that the above preparation methods are merely examples. The persons skilled in the art can obtain other compound structures of the present disclosure through the modifications of the preparation methods.
Device Example 1
[0332] 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. Next, 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 at a vacuum degree of about 10.sup.−8 torr. Compound HI was used as a hole injection layer (HIL). Compound HT was deposited as a hole transport layer (HTL). Compound H1 was used as an electron blocking layer (EBL). The metal complex 1701 of the present disclosure, as a dopant, Compound H1 and Compound H2 were co-deposited as an emissive layer (EML). On the EML, Compound HB was used as a hole blocking layer (HBL). On the HBL, Compound ET and 8-hydroxyquinolinolato-lithium (Liq) were co-deposited as an electron transport layer (ETL). Finally, 8-hydroxyquinolinolato-lithium (Liq) with a thickness of 1 nm was deposited as an electron injection layer, and A1 with a thickness of 120 nm was deposited as a cathode. The device was then transferred back to the glovebox and encapsulated with a glass lid to complete the device.
Device Example 2
[0333] The implementation mode in Device Example 2 was the same as that in Device Example 1, except that the metal complex 1701 of the present disclosure in the EML was replaced with the metal complex 105 of the present disclosure.
Device Comparative Example 1
[0334] The implementation mode in Device Comparative Example 1 was the same as that in Device Example 1, except that the metal complex 1701 of the present disclosure in the emissive layer (EML) was replaced with a compound GD1.
Device Comparative Example 2
[0335] The implementation mode in Device Comparative Example 2 was the same as that in Device Example 1, except that the metal complex 1701 of the present disclosure in the emissive layer (EML) was replaced with a compound GD2.
[0336] Detailed structures and thicknesses of layers of the devices are shown in the following table. The layers using more than one material are obtained by doping different compounds at a weight ratio as recorded in the following stable.
TABLE-US-00002 TABLE 1 Structures of devices of Examples 1 to 2 and Comparative Examples 1 to 2 Device ID HIL HTL EBL EML HBL ETL Example 1 Compound Compound Compound Compound Compound Compound HI HT H1 H1:Compound HB ET:Liq (100 Å) (350 Å) (50 Å) H2:Metal complex (50 Å) (40:60) 1701(63:31:6) (350 Å) (400 Å) Example 2 Compound Compound Compound Compound Compound Compound HI HT H1 H1:Compound HB ET:Liq (100 Å) (350 Å) (50 Å) H2:Metal complex (50 Å) (40:60) 105 (63:31:6) (350 Å) (400 Å) Comparative Compound Compound Compound Compound Compound Compound Example 1 HI HT H1 H1:Compound HB ET:Liq (100 Å) (350 Å) (50 Å) H2:Compound GD1 (50 Å) (40:60) (63:31:6) (350 Å) (400 Å) Comparative Compound Compound Compound Compound Compound Compound Example 2 HI HT H1 H1:Compound HB ET:Liq (100 Å) (350 Å) (50 Å) H2:CompoundGD2 (50 Å) (40:60) (63:31:6) (350 Å) (400 Å)
[0337] The structures of the materials used in the devices are shown as follows:
##STR00074## ##STR00075## ##STR00076##
[0338] The IVL characteristics of the devices were measured. The CIE data, maximum emission wavelength (λ.sub.max), full width at half maximum (FWHM), voltage (V), current efficiency (CE), power efficiency (PE), and external quantum efficiency (EQE) of the devices were measured at 1000 cd/m.sup.2. The data was recorded and shown in Table 2.
TABLE-US-00003 TABLE 2 Device data of Examples 1 to 2 and Comparative Examples 1 to 2 CIE λ.sub.max FWHM Voltage CE PE EQE Device ID (x, y) (nm) (nm) (V) (cd/A) (lm/W) (%) Example 1 (0.358, 0.619) 531 60.4 2.83 105 117 27.45 Example 2 (0.344, 0.633) 531 37.9 2.66 114 135 29.04 Comparative (0.355, 0.622) 531 59.4 3.00 105 110 27.15 Example 1 Comparative (0.351, 0.625) 529 58.3 2.98 103 109 26.64 Example 2
[0339] Discussion:
[0340] Table 2 shows the performance of the devices using the compounds of the present disclosure and comparative compounds. Compared with Comparative Example 1, in Example 1, the ligand L.sub.a of the metal complex contained both fluorine substitution and substitution A at a specific position, the CE of the device was comparable, the EQE was slightly improved, the PE was increased by 6.4%, and the voltage was reduced by 0.17 V. It shows that both fluorine substitution and substitution A at a specific position contained in the ligand L.sub.a can reduce the drive voltage, improve the device efficiency and improve the comprehensive performance of the device.
[0341] Compared with Comparative Example 1, in Example 2, the ligand L.sub.a of the metal complex contained both cyano substitution and substitution A at a specific position, the CE, PE and EQE of the device were increased by 8.5%, 22.7% and 7%, respectively. In addition, the full width at half maximum of Example 2 was narrowed by 21 nm and the voltage was reduced by 0.34 V, compared with Comparative Example 1. It shows that both cyano substitution and substitution A at a specific position contained the ligand L.sub.a can reduce the drive voltage and full width at half maximum, significantly improve the device efficiency and significantly improve the comprehensive performance of the device.
[0342] Compared with Comparative Example 2, in Example 1, the voltage of the device was reduced by 0.15 V, and the CE, PE, and EQE were improved by 1.9%, 7.3% and 3.0%, respectively. Similarly, compared with Comparative Example 2, in Example 2, the voltage of the device was reduced by 0.32 V, the full width at half maximum was narrowed by 20 nm, and the CE, PE, and EQE were improved by 10.7%, 23.9% and 9.0%, respectively.
[0343] The above data show that, in the case that the performances of Comparative Examples have been at a very excellent level, the metal complexes of the present disclosure comprising the ligand L.sub.a having both fluorine or cyano substitution and a specific substituent A at a specific position can obviously surpass the metal complexes of the Comparative Examples in the comprehensive performance of the device and significantly improve the comprehensive performance of the device, which is very rare in the industry.
Device Example 3
[0344] The implementation mode in Device Example 3 was the same as that in Device Example 1, except that the metal complex 1701 of the present disclosure in the emissive layer was replaced with the metal complex 67 of the present disclosure.
Device Example 4
[0345] The implementation mode in Device Example 4 was the same as that in Device Example 1, except that the metal complex 1701 of the present disclosure in the emissive layer was replaced with the metal complex 257 of the present disclosure.
Device Comparative Example 3
[0346] The implementation mode in Device Comparative Example 3 was the same as that in Device Example 1, except that the metal complex 1701 of the present disclosure in the emissive layer (EML) was replaced with a compound GD3.
Device Comparative Example 4
[0347] The implementation mode in Device Comparative Example 4 was the same as that in Device Example 1, except that the metal complex 1701 of the present disclosure in the emissive layer (EML) was replaced with a compound GD4.
Device Comparative Example 5
[0348] The implementation mode in Device Comparative Example 5 was the same as that in Device Example 1, except that the metal complex 1701 of the present disclosure in the emissive layer (EML) was replaced with a compound GD5.
[0349] Detailed structures and thicknesses of layers of the devices are shown in the following table. The layers using more than one material are obtained by doping different compounds at a weight ratio as recorded in the following stable.
TABLE-US-00004 TABLE 3 Structures of devices of Examples 3 to 4 and Comparative Examples 3 to 5 Device ID HIL HTL EBL EML HBL ETL Example 3 Compound Compound Compound Compound Compound Compound HI HT H1 H1:Compound HB ET:Liq (100 Å) (350 Å) (50 Å) H2:Metal complex (50 Å) (40:60) 67(63:31:6) (350 Å) (400 Å) Example 4 Compound Compound Compound Compound Compound Compound HI HT H1 H1:Compound HB ET:Liq (100 Å) (350 Å) (50 Å) H2:Metal complex (50 Å) (40:60) 257(63:31:6) (350 Å) (400 Å) Comparative Compound Compound Compound Compound Compound Compound Example 3 HI HT H1 H1:Compound HB ET:Liq (100 Å) (350 Å) (50 Å) H2:Compound GD3 (50 Å) (40:60) (63:31:6) (350 Å) (400 Å) Comparative Compound Compound Compound Compound Compound Compound Example 4 HI HT H1 H1:Compound HB ET:Liq (100 Å) (350 Å) (50 Å) H2:CompoundGD4 (50 Å) (40:60) (63:31:6) (350 Å) (400 Å) Comparative Compound Compound Compound Compound Compound Compound Example 5 HI HT H1 H1:Compound HB ET:Liq (100 Å) (350 Å) (50 Å) H2:Compound GD5 (50 Å) (40:60) (63:31:6) (350 Å) (400 Å)
[0350] Structures of the new materials used in the device are as follows:
##STR00077## ##STR00078##
[0351] The IVL characteristics of the devices were measured. The CIE data, maximum emission wavelength (λ.sub.max), full width at half maximum (FWHM), voltage (V), current efficiency (CE), power efficiency (PE), and external quantum efficiency (EQE) of the devices were measured at 1000 cd/m.sup.2. The data was recorded and shown in Table 4.
TABLE-US-00005 TABLE 4 Device data of Examples 2 to 4 and Comparative Examples 3 to 5 CIE λ.sub.max FWHM Voltage CE PE EQE Device ID (x, y) (nm) (nm) (V) (cd/A) (lm/W) (%) Example 2 (0.344, 0.633) 531 37.9 2.66 114 135 29.04 Example 3 (0.346, 0.631) 531 39.3 2.68 111 131 28.27 Example 4 (0.347, 0.631) 532 38.2 2.64 113 135 28.94 Comparative (0.346, 0.631) 532 37.4 2.79 106 120 26.90 Example 3 Comparative (0.342, 0.635) 531 35.9 2.70 104 121 26.21 Example 4 Comparative (0.352, 0.627) 534 45.1 2.74 104 119 26.47 Example 5
[0352] Discussion:
[0353] Table 4 shows the performance of the devices using the compounds of the present disclosure and comparative compounds. Compared with Comparative Example 3, in Examples 2 to 4, the ligand L.sub.a of the metal complexes contained both cyano substitution and substituents of different lengths at specific positions, the voltages of the devices were reduced by 0.13 V, 0.11 V and 0.15 V, respectively, the CE of the devices was all improved by around 5%, the PE was increased by 12.5%, 9.2% and 12.5%, respectively, the EQE was improved by around 8.0%, 5.1% and 7.6%, respectively.
[0354] Similarly, compared with Comparative Example 4, in Examples 2 to 4, the ligand L.sub.a of the metal complexes contained both cyano substitution and substituents of different lengths at specific positions, the voltages of the devices were slightly reduced, the CE of the devices was all improved by around 8%, the PE was increased by 11.5%, 8.2% and 11.5%, respectively, and the EQE was improved by around 10.8%, 7.8% and 10.4%, respectively.
[0355] Compared with Comparative Example 5, in Example 2, the ligand L.sub.a of the metal complex contained both a cyano substituent and a substituent A at different substitution positions, the voltage of the device was slightly reduced, the CE, PE and EQE of the device were improved by 9.6%, 13.4% and 9.7%, respectively. Meanwhile, the half peak width was narrowed by 7.2 nm, and the spectrum shows blue shift by 3 nm.
[0356] The above data show that, in the case that the performances of Comparative Examples have been at a very excellent level, the metal complexes of the present disclosure comprising the ligand L.sub.a having both cyano substitution and a specific substituent A at a specific position can significantly improve the comprehensive performance of the device and obviously surpass the metal complexes of the Comparative Examples in the comprehensive performance of the device, which is very rare in the industry.
Device Comparative Example 6
[0357] The implementation mode in Device Comparative Example 6 was the same as that in Device Example 1, except that the metal complex 1701 of the present disclosure in the emissive layer (EML) was replaced with a Compound GD6.
Device Comparative Example 7
[0358] The implementation mode in Device Comparative Example 7 was the same as that in Device Example 1, except that the metal complex 1701 of the present disclosure in the emissive layer (EML) was replaced with a compound GD7.
[0359] Detailed structures and thicknesses of layers of the devices are shown in the following table. The layers using more than one material are obtained by doping different compounds at a weight ratio as recorded in the following stable.
TABLE-US-00006 TABLE 5 Structures of devices of Comparative Examples 6 and 7 Device ID HIL HTL EBL EML HBL ETL Comparative Compound Compound Compound Compound Compound Compound Example 6 HI HT H1 H1:Compound HB ET:Liq (100 Å) (350 Å) (50 Å) H2:Compound GD6 (50 Å) (40:60) (63:31:6) (350 Å) (400 Å) Comparative Compound Compound Compound Compound Compound Compound Example 7 HI HT H1 H1:Compound HB ET:Liq (100 Å) (350 Å) (50 Å) H2:Compound GD7 (50 Å) (40:60) (63:31:6) (350 Å) (400 Å)
[0360] Structures of the new materials used in the device are as follows:
##STR00079##
[0361] The IVL characteristics of the devices were measured. The CIE data, maximum emission wavelength (λ.sub.max), full width at half maximum (FWHM), voltage (V), current efficiency (CE), power efficiency (PE), and external quantum efficiency (EQE) of the devices were measured at 1000 cd/m.sup.2. The data was recorded and shown in Table 6.
TABLE-US-00007 TABLE 6 Device data of Example 1 and Comparative Examples 6 and 7 CIE λ.sub.max FWHM Voltage CE PE EQE Device ID (x, y) (nm) (nm) (V) (cd/A) (lm/W) (%) Example 1 (0.358, 0.619) 531 60.4 2.83 105 117 27.45 Comparative (0.340, 0.629) 527 60.3 2.84 92 102 24.21 Example 6 Comparative (0.352, 0.624) 530 58.4 3.06 96 98 24.75 Example 7
[0362] Discussion:
[0363] Table 6 shows the performance of the devices using the compounds of the present disclosure and comparative compounds. Compared with Comparative Examples 6 and 7, in
[0364] Example 1, the ligand L.sub.a of the metal complex contained both fluorine substitution and substituents of different lengths at specific positions. Compared with Comparative Example 6, in Example 1, the voltage of the device was equivalent, and the CE, PE, and EQE were improved by 14.1%, 14.7% and 13.4%, respectively. Similarly, compared with Comparative Example 7, in Example 1, the voltage of the device was reduced by 0.23 V, and the CE, PE, and EQE were improved by 9.4%, 19.4% and 10.9%, respectively.
[0365] In sum, in the case that the performances of Comparative Examples have been at a very excellent level, the metal complexes of the present disclosure comprising the ligand L.sub.a having both fluorine substitution and a specific substituent A at a specific position can obviously surpass the metal complexes of the Comparative Examples in the comprehensive performance of the device and significantly improve the comprehensive performance of the device, which is very rare in the industry.
[0366] As can be seen from Examples and Comparative Examples in the above discussion, compared with metal complexes of Comparative Examples, the metal complex of the present disclosure comprising the ligand L.sub.a having both cyano or fluorine substitution and substitution A at a specific position can significantly improve the device performance. The observed advantages of the compounds of the present disclosure are completely unexpected. Even for the persons skilled in the art, it is impossible to predict this situation.
[0367] It should be understood that various embodiments described herein are merely examples and not intended to limit the scope of the present disclosure. Therefore, it is apparent to the persons skilled in the art that the present disclosure as claimed may include variations from specific embodiments and preferred embodiments described herein. Many of materials and structures described herein may be substituted with other materials and structures without departing from the spirit of the present disclosure. It should be understood that various theories as to why the present disclosure works are not intended to be limitative.