Organic light-emitting materials containing cyano-substituted ligand
An organic light-emitting material containing cyano-substituted ligand is disclosed. The organic light-emitting material is a metal complex containing a cyano-substituted ligand, which can be used as a light-emitting material in a light-emitting layer of an organic electroluminescent device. These new complexes can provide better device performance, e.g., narrower full width at half maximum, lower voltage values, and higher quantum efficiency, and the like. An electroluminescent device and a compound formulation containing the metal complex, and a compound capable of being used to prepare the metal complex are also disclosed.
1. A metal complex comprising a ligand L a represented by Formula 1:
wherein,
Cy is any structure selected from the group consisting of:
R may represent mono-substitution, up to the maximum available multi-substitution, or no substitution; when more than one R exists in any structure, the R may be the same or different;
X 1 to X 4 are each independently selected from C, CR x1 or N, and at least one of X 1 to X 4 is C which is connected to the Cy; when more than one of X 1 to X 4 is CR x1 , the R x1 may be the same or different;
X 5 to X 8 are each independently selected from CR x2 or N; when more than one of X 5 to X 8 is CR x2 , the R x2 may be the same or different;
X is selected from the group consisting of O, S, Se, NR x3 , CR x4 R x5 and SiR x6 R x7 ;
R, R x1 , R x2 , R x3 , R x4 , R x5 , R x6 and R x7 are each independently selected from the group consisting of hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1-20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3-20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1-20 carbon atoms, a substituted or unsubstituted arylalkyl group having 7-30 carbon atoms, a substituted or unsubstituted alkoxy group having 1-20 carbon atoms, a substituted or unsubstituted aryloxy group having 6-30 carbon atoms, a substituted or unsubstituted alkenyl group having 2-20 carbon atoms, a substituted or unsubstituted aryl group having 6-30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3-30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3-20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6-20 carbon atoms, a substituted or unsubstituted amino group having 0-20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, thioalkyl, sulfinyl, sulfonyl, phosphino, and combinations thereof,
wherein, at least one of R x1 and R x2 is present and is a cyano group;
wherein, “#” represents a position at which the metal is connected, and “*” represents a position at which X 1 , X 2 , X 3 or X 4 is connected;
any two adjacent substituents can optionally be joined to form a ring;
X 1 , X 2 , X 3 or X 4 is connected to the metal through a metal-carbon bond or a metal-nitrogen bond.
2. The metal complex according to claim 1 , wherein Cy is any structure selected from the group consisting of:
wherein,
R may represent mono-substitution, up to the maximum available multi-substitution, or no substitution; when more than one R exists in any structure, the R may be the same or different;
R is each independently selected from the group consisting of hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1-20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3-20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1-20 carbon atoms, a substituted or unsubstituted arylalkyl group having 7-30 carbon atoms, a substituted or unsubstituted alkoxy group having 1-20 carbon atoms, a substituted or unsubstituted aryloxy group having 6-30 carbon atoms, a substituted or unsubstituted alkenyl group having 2-20 carbon atoms, a substituted or unsubstituted aryl group having 6-30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3-30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3-20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6-20 carbon atoms, a substituted or unsubstituted amino group having 0-20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, thioalkyl, sulfinyl, sulfonyl, phosphino, and combinations thereof,
any two adjacent substituents can optionally be joined to form a ring;
wherein, “#” represents a position at which the metal is connected, and “*” represents a position at which X 1 , X 2 , X 3 or X 4 is connected.
3. The metal complex according to claim 1 , wherein the metal complex has a general formula of M(L a ) m (L b ) n (L c ) q , wherein L a is a first ligand coordinated to the metal M, and the L b and the L c are a second ligand and a third ligand coordinated to the metal M, respectively, the L b and the L c may be the same or different;
the L a , L b and L c can optionally be linked to form a multidentate ligand;
wherein, m is 1, 2 or 3, n is 0, 1 or 2, q is 0, 1 or 2, and m+n+q is equal to the oxidation state of M;
wherein, the metal M is selected from the group consisting of Cu, Ag, Au, Ru, Rh, Pd, Os, Ir, and Pt;
wherein, L a is independently selected from the group consisting of:
X is selected from the group consisting of O, S, Se, NR x3 , CR x4 R x5 and SiR x6 R x7 ;
R 1 , R 2 , R 3 and R 4 may represent mono-, di-, tri- or tetra-substitution, or no substitution;
R 1 , R 2 , R 3 , R 4 , R x3 , R x4 , R x5 , R x6 and R x7 are each independently selected from the group consisting of hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1-20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3-20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1-20 carbon atoms, a substituted or unsubstituted arylalkyl group having 7-30 carbon atoms, a substituted or unsubstituted alkoxy group having 1-20 carbon atoms, a substituted or unsubstituted aryloxy group having 6-30 carbon atoms, a substituted or unsubstituted alkenyl group having 2-20 carbon atoms, a substituted or unsubstituted aryl group having 6-30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3-30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3-20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6-20 carbon atoms, a substituted or unsubstituted amino group having 0-20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, thioalkyl, sulfinyl, sulfonyl, phosphino, and combinations thereof,
wherein, at least one of R 3 and R 4 is present and is a cyano group;
any two adjacent substituents can optionally be joined to form a ring;
wherein, the L b and L c are each independently selected from the group consisting of:
wherein,
R a , R b , and R c may represent mono-, di-, tri- or tetra-substitution, or no substitution;
X b is selected from the group consisting of: O, S, Se, NR N1 , and CR C1 R C2 ;
R a , R b , R c , R N1 , R C1 and R C2 are each independently selected from the group consisting of hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1-20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3-20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1-20 carbon atoms, a substituted or unsubstituted arylalkyl group having 7-30 carbon atoms, a substituted or unsubstituted alkoxy group having 1-20 carbon atoms, a substituted or unsubstituted aryloxy group having 6-30 carbon atoms, a substituted or unsubstituted alkenyl group having 2-20 carbon atoms, a substituted or unsubstituted aryl group having 6-30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3-30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3-20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6-20 carbon atoms, a substituted or unsubstituted amino group having 0-20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, thioalkyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and
any two adjacent substituents can optionally be joined to form a ring.
4. The metal complex according to claim 3 , wherein the metal complex has a structure represented by any one of Formulas 2 to 10:
wherein,
m is 1, 2 or 3;
X is selected from O, S or Se;
R 1 , R 3 , and R 4 may represent mono-, di-, tri- or tetra-substitution, or no substitution;
R a , R b , and R c may represent mono-, di-, tri- or tetr-substitution, or no substitution;
R 1 , R 3 , R 4 , R a , R b and R c are each independently selected from the group consisting of hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1-20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3-20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1-20 carbon atoms, a substituted or unsubstituted arylalkyl group having 7-30 carbon atoms, a substituted or unsubstituted alkoxy group having 1-20 carbon atoms, a substituted or unsubstituted aryloxy group having 6-30 carbon atoms, a substituted or unsubstituted alkenyl group having 2-20 carbon atoms, a substituted or unsubstituted aryl group having 6-30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3-30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3-20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6-20 carbon atoms, a substituted or unsubstituted amino group having 0-20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, thioalkyl, sulfinyl, sulfonyl, phosphino, and combinations thereof;
wherein, at least one of R 3 and R 4 is present and is a cyano group;
any two adjacent substituents can optionally be joined to form a ring.
5. The metal complex according to claim 4 , wherein the metal complex has a structure of Formula 2-a:
wherein,
m is 1, 2 or 3;
X is selected from O, S or Se;
R 3 , and R 4 may represent mono-, di-, tri- or tetra-substitution, or no substitution;
R a , R b , and R c may represent mono-, di-, tri- or tetra-substitution, or no substitution;
wherein, R 11 , R 12 , R 13 , R 14 , R 3 , R 4 , R a , and R b are each independently selected from the group consisting of hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1-20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3-20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1-20 carbon atoms, a substituted or unsubstituted arylalkyl group having 7-30 carbon atoms, a substituted or unsubstituted alkoxy group having 1-20 carbon atoms, a substituted or unsubstituted aryloxy group having 6-30 carbon atoms, a substituted or unsubstituted alkenyl group having 2-20 carbon atoms, a substituted or unsubstituted aryl group having 6-30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3-30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3-20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6-20 carbon atoms, a substituted or unsubstituted amino group having 0-20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, thioalkyl, sulfinyl, sulfonyl, phosphino, and combinations thereof,
wherein, at least one of R 3 and R 4 is present and is a cyano group;
any two adjacent substituents can optionally be joined to form a ring.
6. The metal complex according to claim 1 , wherein at least one of X 5 to X 8 in Formula 1 is CR x2 , and the R x2 is a cyano group.
7. The metal complex according to claim 4 , wherein R 4 may represent mono-, di-, tri- or tetra-substitution; when more than one R 4 exists, the R 4 may be the same or different; R 4 is selected from the group consisting of deuterium, halogen, a substituted or unsubstituted alkyl group having 1-20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3-20 ring carbon atoms, a substituted or unsubstituted aryl group having 6-30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3-30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3-20 carbon atoms, a cyano group, and combinations thereof; and at least one R 4 is a cyano group.
8. The metal complex according to claim 3 , wherein the ligand L a is selected from the group consisting of:
9. The metal complex according to claim 8 , wherein the L a can be partially or fully deuterated.
10. The metal complex according to claim 9 , wherein the ligand L a is selected from the group consisting of:
11. The metal complex according to claim 3 , wherein the metal complex has the Formula IrL a (L b ) 2 or Ir(L a ) 2 L b , wherein L a is one or two selected from L a1 to L a109 , and L b is one or two selected from the group consisting of:
12. The metal complex according to claim 3 , wherein the metal complex has the Formula Ir(L a ) 2 L c or IrL a (L c ) 2 , wherein L a is one or two selected from L a1 to L a109 , and L c is one or two selected from the group consisting of:
13. The metal complex according to claim 1 , wherein the metal complex has a structure represented by any one selected from the group consisting of Metal complex 1 to Metal complex 316:
wherein, Metal complex 1 to Metal complex 226 have the structure of IrL a (L b ) 2 , wherein two L b are the same, wherein L a and L b correspond to the structures as shown in the following table, respectively:
Metal
Metal
complex
L a
L b
complex
L a
L b
1
L a1
L b1
2
L a2
L b1
3
L a3
L b1
4
L a4
L b1
5
L a121
L b1
6
L a122
L b1
7
L a123
L b1
8
L a137
L b1
9
L a138
L b1
10
L a139
L b1
11
L a153
L b1
12
L a154
L b1
13
L a155
L b1
14
L a169
L b1
15
L a170
L b1
16
L a171
L b1
17
L a221
L b1
18
L a222
L b1
19
L a293
L b1
20
L a294
L b1
21
L a295
L b1
22
L a297
L b1
23
L a298
L b1
24
L a299
L b1
25
L a313
L b1
26
L a314
L b1
27
L a415
L b1
28
L a416
L b1
29
L a467
L b1
30
L a468
L b1
31
L a487
L b1
32
L a488
L b1
33
L a507
L b1
34
L a508
L b1
35
L a516
L b1
36
L a517
L b1
37
L a527
L b1
38
L a528
L b1
39
L a547
L b1
40
L a548
L b1
41
L a576
L b1
42
L a577
L b1
43
L a592
L b1
44
L a593
L b1
45
L a640
L b1
46
L a652
L b1
47
L a692
L b1
48
L a693
L b1
49
L a704
L b1
50
L a842
L b1
51
L a854
L b1
52
L a896
L b1
53
L a962
L b1
54
L a966
L b1
55
L a970
L b1
56
L a973
L b1
57
L a974
L b1
58
L a975
L b1
59
L a976
L b1
60
L a978
L b1
61
L a985
L b1
62
L a987
L b1
63
L a988
L b1
64
L a999
L b1
65
L a1003
L b1
66
L a1010
L b1
67
L a1
L b3
68
L a2
L b3
69
L a3
L b3
70
L a4
L b3
71
L a121
L b3
72
L a122
L b3
73
L a123
L b3
74
L a137
L b3
75
L a138
L b3
76
L a139
L b3
77
L a293
L b3
78
L a294
L b3
79
L a297
L b3
80
L a298
L b3
81
L a576
L b3
82
L a577
L b3
83
L a592
L b3
84
L a593
L b3
85
L a640
L b3
86
L a652
L b3
87
L a692
L b3
88
L a693
L b3
89
L a704
L b3
90
L a842
L b3
91
L a854
L b3
92
L a896
L b3
93
L a962
L b3
94
L a966
L b3
95
L a970
L b3
96
L a973
L b3
97
L a974
L b3
98
L a975
L b3
99
L a976
L b3
100
L a978
L b3
101
L a985
L b3
102
L a987
L b3
103
L a988
L b3
104
L a999
L b3
105
L a1003
L b3
106
L a1010
L b3
107
L a1
L b4
108
L a2
L b4
109
L a3
L b4
110
L a4
L b4
111
L a121
L b4
112
L a122
L b4
113
L a123
L b4
114
L a137
L b4
115
L a138
L b4
116
L a139
L b4
117
L a293
L b4
118
L a294
L b4
119
L a297
L b4
120
L a298
L b4
121
L a576
L b4
122
L a577
L b4
123
L a592
L b4
124
L a593
L b4
125
L a640
L b4
126
L a652
L b4
127
L a692
L b4
128
L a693
L b4
129
L a704
L b4
130
L a842
L b4
131
L a854
L b4
132
L a896
L b4
133
L a962
L b4
134
L a966
L b4
135
L a970
L b4
136
L a973
L b4
137
L a974
L b4
138
L a975
L b4
139
L a976
L b4
140
L a978
L b4
141
L a985
L b4
142
L a987
L b4
143
L a988
L b4
144
L a999
L b4
145
L a1003
L b4
146
L a1010
L b4
147
L a1
L b8
148
L a2
L b8
149
L a3
L b8
150
L a4
L b8
151
L a121
L b8
152
L a122
L b8
153
L a123
L b8
154
L a137
L b8
155
L a138
L b8
156
L a139
L b8
157
L a293
L b8
158
L a294
L b8
159
L a297
L b8
160
L a298
L b8
161
L a576
L b8
162
L a577
L b8
163
L a592
L b8
164
L a593
L b8
165
L a640
L b8
166
L a652
L b8
167
L a692
L b8
168
L a693
L b8
169
L a704
L b8
170
L a842
L b8
171
L a854
L b8
172
L a896
L b8
173
L a962
L b8
174
L a966
L b8
175
L a970
L b8
176
L a973
L b8
177
L a974
L b8
178
L a975
L b8
179
L a976
L b8
180
L a978
L b8
181
L a985
L b8
182
L a987
L b8
183
L a988
L b8
184
L a999
L b8
185
L a1003
L b8
186
L a1010
L b8
187
L a1
L b30
188
L a2
L b30
189
L a3
L b30
110
L a4
L b30
191
L a121
L b30
192
L a122
L b30
193
L a123
L b30
194
L a137
L b30
195
L a138
L b30
196
L a139
L b30
197
L a293
L b30
198
L a294
L b30
199
L a297
L b30
200
L a298
L b30
201
L a576
L b30
202
L a577
L b30
203
L a592
L b30
204
L a593
L b30
205
L a640
L b30
206
L a652
L b30
207
L a692
L b30
208
L a693
L b30
209
L a704
L b30
210
L a842
L b30
211
L a854
L b30
212
L a896
L b30
213
L a962
L b30
214
L a966
L b30
215
L a970
L b30
216
L a973
L b30
217
L a974
L b30
218
L a975
L b30
219
L a976
L b30
220
L a978
L b30
221
L a985
L b30
222
L a987
L b30
223
L a988
L b30
224
L a999
L b30
225
L a1003
L b30
226
L a1010
L b30
wherein, Metal complex 227 to Metal complex 274 have the structure of Ir(L a ) 2 L c , wherein two L a are the same, wherein L a and L c correspond to the structures as shown in the following table, respectively:
Metal
Metal
complex
L a
L c
complex
L a
L c
227
L a323
L c1
228
L a324
L c1
229
L a328
L c1
230
L a329
L c1
231
L a333
L c1
232
L a334
L c1
233
L a338
L c1
234
L a339
L c1
235
L a343
L c1
236
L a344
L c1
237
L a348
L c1
238
L a349
L c1
239
L a353
L c1
240
L a354
L c1
241
L a358
L c1
242
L a359
L c1
243
L a363
L c1
244
L a364
L c1
245
L a368
L c1
246
L a369
L c1
247
L a373
L c1
248
L a374
L c1
249
L a388
L c1
250
L a389
L c1
251
L a323
L 31
252
L a324
L 31
253
L a328
L 31
254
L a329
L 31
255
L a333
L 31
256
L a334
L 31
257
L a338
L 31
258
L a339
L 31
259
L a343
L 31
260
L a344
L 31
261
L a348
L 31
262
L a349
L 31
263
L a353
L 31
264
L a354
L 31
265
L a358
L 31
266
L a359
L 31
267
L a363
L 31
268
L a364
L 31
269
L a368
L 31
270
L a369
L 31
271
L a373
L 31
272
L a374
L 31
273
L a388
L 31
274
L a389
L 31
wherein, Metal complex 275 to Metal complex 316 have the structure of Ir(L a ) 3 , wherein three L a are the same, wherein L a corresponds to the structures as shown in the following table:
Metal
complex
L a
275
L a1
276
L a2
277
L a3
278
L a121
279
L a122
280
L a137
281
L a138
282
L a293
283
L a297
284
L a298
285
L a487
286
L a488
287
L a507
288
L a508
289
L a547
290
L a548
291
L a576
292
L a577
293
L a640
294
L a641
295
L a652
296
L a653
297
L a692
298
L a693
299
L a704
300
L a842
301
L a854
302
L a896
303
L a962
304
L a966
305
L a970
306
L a973
307
L a974
308
L a975
309
L a976
310
L a978
311
L a985
312
L a987
313
L a988
314
L a999
315
L a1003
316
L a1010 .
14. A compound selected from the group consisting of:
15. An electroluminescent device comprising:
an anode,
a cathode, and
an organic layer disposed between the anode and the cathode, wherein the organic layer includes the metal complex according to claim 1 .
16. The electroluminescent device according to claim 15 , wherein the organic layer is a light emitting layer, and the metal complex is a light emitting material.
17. The electroluminescent device according to claim 16 , wherein the organic layer further comprises a host material; or wherein the organic layer contains at least two host materials.
18. The electroluminescent device according to claim 17 , wherein the host material comprises at least one chemical group selected from the group consisting of benzene, biphenyl, pyridine, pyrimidine, triazine, carbazole, azacarbazole, indolocarbazole, dibenzothiophene, azadibenzothiophen, dibenzofuran, azadibenzofuran, dibenzoselenophene, azadibenzoselenophene, triphenylene, azatriphenylene, fluorene, silicon-fluorene, naphthalene, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene, azaphenanthrene, and combinations thereof.
19. The electroluminescent device according to claim 15 , wherein the electroluminescent device is incorporated into a device selected from the group consisting of a consumption product, an electronic component module, an organic light-emitting device and a lighting panel.
20. A compound formulation comprising the metal complex according to claim 1 .
21. The metal complex according to claim 5 , when R 11 and R 14 are both hydrogen, R 12 and R 13 are each independently selected from the group consisting of hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1-20 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1-20 carbon atoms, a substituted or unsubstituted alkoxy group having 1-20 carbon atoms, a substituted or unsubstituted amino group having 0-20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, thioalkyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and the sum of carbon atoms in R 12 and R 13 is less than or equal to 1;
alternatively, when at least one of R 11 and R 14 is not hydrogen, R 12 and R 13 are each independently selected from the group consisting of hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1-20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3-20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1-20 carbon atoms, a substituted or unsubstituted arylalkyl group having 7-30 carbon atoms, a substituted or unsubstituted alkoxy group having 1-20 carbon atoms, a substituted or unsubstituted aryloxy group having 6-30 carbon atoms, a substituted or unsubstituted alkenyl group having 2-20 carbon atoms, a substituted or unsubstituted aryl group having 6-30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3-30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3-20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6-20 carbon atoms, a substituted or unsubstituted amino group having 0-20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, thioalkyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
22. The metal complex according to claim 9 , wherein the hydrogen on the aryl group in the L a can be partially or fully deuterated; or the hydrogen on the alkyl group in the L a may be partially or fully deuterated.