TWI724829B - 一種咪唑並氮雜環化合物及其應用 - Google Patents

一種咪唑並氮雜環化合物及其應用 Download PDF

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TWI724829B
TWI724829B TW109109688A TW109109688A TWI724829B TW I724829 B TWI724829 B TW I724829B TW 109109688 A TW109109688 A TW 109109688A TW 109109688 A TW109109688 A TW 109109688A TW I724829 B TWI724829 B TW I724829B
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鄢亮亮
戴雷
蔡麗菲
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大陸商廣東阿格蕾雅光電材料有限公司
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Abstract

本發明涉及一種咪唑並氮雜環化合物及其應用。本發明化合物具有式(I)所示結構。本發明咪唑並氮雜環化合物具有昇華溫度低，光、電、熱穩定性好，折射率高、可見光區折射率差異小等優點，該化合物製備的器件具有電壓低、壽命長，發光效率高等優點，可用於有機發光器件中。特別是作為電子傳輸材料、空穴阻隔層材料、光提取層材料，具有應用於AMOLED產業的可能。

Description

一種咪唑並氮雜環化合物及其應用
本發明涉及有機電致發光材料技術領域，特別涉及咪唑並氮雜環化合物及其在有機電致發光器件上的應用。
目前，作為新一代顯示技術的有機電致發光器件（OLED）在顯示和照明技術方面都獲得了越來越多的關注，應用前景十分廣泛。但是，和市場應用要求相比，OLED器件的發光效率、驅動電壓、使用壽命等性能還需要繼續加強和改進。
一般來說，OLED器件基本結構為在金屬電極中間夾雜各種不同功能的有機功能材料薄膜，猶如一個三明治的結構，在電流的驅動下，從陰陽兩極分別注入空穴和電子，空穴和電子在移動一段距離後，在發光層得到複合，並以光或熱的形式進行釋放，從而產生了OLED的發光。然而，有機功能材料是有機電致發光器件的核心組成部分，材料的熱穩定性、光化學穩定性、電化學穩定性、量子產率、成膜穩定性、結晶性、色飽和度等都是影響器件性能表現的主要因素。
一方面，如何縮小OLED器件內外量子效率之間的巨大差距，如何減少器件中的全發射效應、提高光耦合提取比例引起人們的廣泛關注。現行的光提取層的材料的折射率都比較低，尤其是在紅光波段，通常折射率小於1.85，極少數大於1.90，更少數大於2.0。另外，現有的光提取材料在紅綠藍光波段區域的折射率差別較大，造成三種顏色光的最佳厚度差別大，未能充分體現光提取材料的性能。對於頂發射器件來說，光提取層材料的折射率越大，相應的外量子效率就越高，器件的發光效率就越高。所以，開發高折射率的光提取層材料尤為重要。CN103828485和TW201506128公開了以多聯苯二胺為核心的光提取層材料，但是折射率還是稍微偏低，尤其是在紅光方面更需要進一步提升。
另一方面，如何降低器件工作電壓、降低產品功耗、提高器件壽命、提高發光效率，也是OLED器件不斷提升的方向。CN101186608公開了一例以咪唑並吡啶和蒽環鍵接的化合物，這類化合物三線態能級、玻璃化轉變溫度和器件壽命都需要得到改善。邱等在CN103709180、CN103709181、CN103788087、CN103788116公開了一系列以咪唑並吡啶和稠合芳環鍵接的化合物，這類化合物的三線態能級、玻璃化轉變溫度和器件壽命也需要進一步改善。
針對上述領域中的缺陷，本發明提供一種咪唑並氮雜環化合物，所述化合物具有式I所示結構。該類化合物具有昇華溫度低，光、電、熱穩定性好，折射率高、可見光區折射率差異小等優點，可用於有機發光器件中。
本發明還提供該咪唑並氮雜環化合物在OLED中的應用，特別是作為電子傳輸材料、空穴阻隔層材料、光提取層材料，使器件具有發光效率高，電壓低、壽命長的特點，具有應用於AMOLED產業的可能。
一種化合物，其結構式如式（I）所示：
Figure 02_image001
（I） 其中R1為單鍵、烷基、雜烷基、環烷基、取代或未取代的C6-C30的非稠環芳基、取代或未取代的C3-C27的非稠環雜芳基； 其中R2、R3、R4獨立的選自氫、氘、鹵素、烷基、雜烷基、環烷基、烷氧基、芳氧基、氨基、矽烷基、腈、異腈、膦基、取代或未取代的C6-C60的芳基、取代或未取代的C1-C60的雜芳基、經取代或未經取代的單環或多環C3-C60脂肪族環或芳香族環且R3、R4中至少有一個為取代或未取代的C6-C60的芳基、取代或未取代的C1-C60的雜芳基、經取代或未經取代的單環或多環C3-C60脂肪族環或芳香族環，其中雜烷基或雜芳基中的一個或多個碳原子可由選自O、S、N、Se、Si、Ge中的至少一個雜原子替換；所述取代為被氘、鹵素、C1-C30烷基、C1-C30雜烷基、C3-C30環烷基、氨基、矽烷基、腈、異腈、、膦基、C6-C60的芳基、C1-C60的雜芳基取代； 其中X1、X2、X3獨立的表示為CH或者N； X4、X5、X6獨立的表示為CR0或者N，R0獨立的選自氫、氘、鹵素、烷基、雜烷基、芳烷基、烷氧基、芳氧基、氨基、矽烷基、芳基、雜芳基、腈、異腈、膦基，且相鄰的R0能鍵接成並環。
優選：其中R1為單鍵、C1-C30烷基、C1-C30雜烷基、C3-C30環烷基、取代或未取代的C6-C30的非稠環芳基、取代或未取代的C3-C27的非稠環雜芳基； 其中R2、R3、R4獨立的選自氫、氘、鹵素、C1-C30烷基、C1-C30雜烷基、C3-C30環烷基、氨基、矽烷基、腈、異腈、膦基、取代或未取代的C6-C60的芳基、取代或未取代的C1-C60的雜芳基、經取代或未經取代的單環或多環C3-C60脂肪族環或芳香族環且R3、R4中至少有一個為取代或未取代的C6-C60的芳基、取代或未取代的C1-C60的雜芳基、經取代或未經取代的單環或多環C3-C60脂肪族環或芳香族環，其中雜烷基或雜芳基中的一個或多個碳原子由選自O、S、N中的至少一個雜原子替換；所述取代為被氘、鹵素、C1-C30烷基、C1-C30雜烷基、C3-C30環烷基、氨基、矽烷基、腈、異腈、、膦基、C6-C60的芳基、C1-C60的雜芳基取代； 其中X1、X2、X3獨立的表示為CH或者N； X4、X5、X6獨立的表示為CR0或者N，R0獨立的選自氫、氘、鹵素、C1-C30烷基、C1-C30雜烷基、芳烷基、氨基、矽烷基、芳基、雜芳基、腈、異腈、膦基，且相鄰的R0能鍵接成並環。
進一步優選： 其中X1、X2、X3至少一個是N。
再優選：其中R3或R4至少之一含有以下結構式（II），其中R1為單鍵、烷基、雜烷基、環烷基、C1-C30烷基取代或未取代的C6-C30的非稠環芳基、C1-C30烷基取代或未取代的C3-C27的非稠環雜芳基；其中R2為氫、氘、鹵素、烷基、雜烷基、環烷基、C1-C30烷基取代或未取代的C6-C60的芳基、C1-C30烷基取代或未取代的C1-C60的雜芳基
Figure 02_image003
式（II ）                       。
更優選：其中R3、R4中一個為式（II）結構，另一個為C1-C4烷基取代或未取代的C6-C18的芳基、C1-C4烷基取代或未取代的C3-C15的雜芳基；R1為C1-C4烷基取代或未取代的C6-C18的非稠環芳基、C1-C4烷基取代或未取代的C3-C15的非稠環雜芳基；R2為C1-C4烷基取代或未取代的C6-C18的芳基、C1-C4烷基取代或未取代的C3-C15的雜芳基。
優選：根據權利要求5所述的化合物，其中R1為C6-C18的非稠環芳基或C5-C15的非稠環雜芳基；R2為C6-C18的芳基或C5-C15的雜芳基。
作為優選的化合物為以下化合物：
A 1 A 2 A 3
Figure 02_image005
Figure 02_image007
Figure 02_image009
A 4 A 5 A 6
Figure 02_image011
Figure 02_image013
Figure 02_image015
A 7 A 8 A 9
Figure 02_image017
Figure 02_image019
Figure 02_image021
A 10 A 11 A 12
Figure 02_image023
Figure 02_image025
Figure 02_image027
A 13 A 14 A 15
Figure 02_image029
Figure 02_image031
Figure 02_image033
A 16 A 17 A 18
Figure 02_image035
Figure 02_image037
Figure 02_image039
A 19 A 20 A 21
Figure 02_image041
Figure 02_image043
Figure 02_image045
A 22 A 23 A 24
Figure 02_image047
Figure 02_image049
Figure 02_image051
A 25 A 26 A 27
Figure 02_image053
Figure 02_image055
Figure 02_image057
A 28 A 29 A 30
Figure 02_image059
Figure 02_image061
Figure 02_image063
A 31 A 32 A 33
Figure 02_image065
Figure 02_image067
Figure 02_image069
A 34 A 35 A 36
Figure 02_image071
Figure 02_image073
Figure 02_image075
A 37 A 38 A 39
Figure 02_image077
Figure 02_image079
Figure 02_image081
A 40 A 41 A 42
Figure 02_image083
Figure 02_image085
Figure 02_image087
A 43 A 44 A 45
Figure 02_image089
Figure 02_image091
Figure 02_image093
A 46 A 47 A 48
Figure 02_image095
Figure 02_image097
Figure 02_image099
A 49 A 50 A 51
Figure 02_image101
Figure 02_image103
Figure 02_image105
A 52 A 53 A 54
Figure 02_image107
Figure 02_image109
Figure 02_image111
A 55 A 56 A 57
Figure 02_image113
Figure 02_image115
Figure 02_image117
A 58 A 59 A 60
Figure 02_image119
Figure 02_image121
Figure 02_image123
A 61 A 62 A 63
Figure 02_image125
Figure 02_image127
Figure 02_image129
A 64 A 65 A 66
Figure 02_image131
Figure 02_image133
Figure 02_image135
A 67 A 68 A 69
Figure 02_image137
Figure 02_image139
Figure 02_image141
A 70 A 71 A 72
Figure 02_image143
Figure 02_image145
Figure 02_image147
A 73 A 74 A 75
Figure 02_image149
Figure 02_image151
Figure 02_image153
A 76 A 77 A 78
Figure 02_image155
Figure 02_image157
Figure 02_image159
A 79 A 80 A 81
Figure 02_image161
Figure 02_image163
Figure 02_image165
A 82 A 83 A 84
Figure 02_image167
Figure 02_image169
Figure 02_image171
A 85 A 86 A 87
Figure 02_image173
Figure 02_image175
Figure 02_image177
A 88 A 89 A 90
Figure 02_image179
Figure 02_image181
Figure 02_image183
A 91 A 92 A 93
Figure 02_image185
Figure 02_image187
Figure 02_image189
A 94 A 95 A 96
Figure 02_image191
Figure 02_image193
Figure 02_image195
A 97 A 98 A 99
Figure 02_image197
Figure 02_image199
   
Figure 02_image201
  。
優選：式（I）所述化合物，其中X1、X2、X3表示為CH。
進一步優選：其中R1為單鍵、C1-C30烷基取代或未取代的C6-C30的非稠環芳基、C1-C30烷基取代或未取代的C3-C27的非稠環雜芳基；其中R2為C1-C30烷基取代或未取代的C6-C60的芳基、C1-C30烷基取代或未取代的C1-C60的雜芳基；R3、R4為氫、氘、鹵素、烷基、雜烷基、環烷基、C1-C30烷基取代或未取代的C6-C60的芳基、C1-C30烷基取代或未取代的C1-C60的雜芳基、經取代或未經取代的單環或多環C3-C60脂肪族環或芳香族環且R3、R4中至少有一個為C1-C30烷基取代或未取代的C6-C60的芳基、C1-C30烷基取代或未取代的C1-C60的雜芳基、經取代或未經取代的單環或多環C3-C60脂肪族環或芳香族環。
再優選：其中R1為單鍵、C1-C4烷基取代或未取代的C6-C18的非稠環芳基、C1-C4烷基取代或未取代的C3-C15的非稠環雜芳基；R2為C1-C4烷基取代或未取代的C6-C18的芳基、C1-C4烷基取代或未取代的C3-C15的雜芳基；R3、R4為氫、氘、鹵素、烷基、C1-C4烷基取代或未取代的C6-C18的芳基、C1-C4烷基取代或未取代的C3-C15的雜芳基、經取代或未經取代的單環或多環C3-C18脂肪族環或芳香族環且R3、R4不同。
更優選：其中R1為單鍵、C6-C18的非稠環芳基或C3-C15的非稠環雜芳基；R2為C6-C18的芳基或C3-C15的雜芳基。
作為優選的化合物為以下化合物：
B 1 B 2 B 3
Figure 02_image203
Figure 02_image205
Figure 02_image207
B 4 B 5 B 6
Figure 02_image209
Figure 02_image211
Figure 02_image213
B 7 B 8 B 9
Figure 02_image215
Figure 02_image217
Figure 02_image219
B 10 B 11 B 12
Figure 02_image221
Figure 02_image223
Figure 02_image225
B 13 B 14 B 15
Figure 02_image227
Figure 02_image229
Figure 02_image231
B 16 B 17 B 18
Figure 02_image233
Figure 02_image235
Figure 02_image237
B 19 B 20 B 21
Figure 02_image239
Figure 02_image241
Figure 02_image243
B 22 B 23 B 24
Figure 02_image245
Figure 02_image247
Figure 02_image249
B 25 B 26 B 27
Figure 02_image251
Figure 02_image253
Figure 02_image255
B 28 B 29 B 30
Figure 02_image257
Figure 02_image259
Figure 02_image261
B 31 B 32 B 33
Figure 02_image263
Figure 02_image265
Figure 02_image267
B 34 B 35 B 36
Figure 02_image269
Figure 02_image271
Figure 02_image273
B 37 B 38 B 39
Figure 02_image275
Figure 02_image277
Figure 02_image279
B 40 B 41 B 42
Figure 02_image281
Figure 02_image283
Figure 02_image285
B 43 B 44 B 45
Figure 02_image287
Figure 02_image289
Figure 02_image291
B 46 B 47 B 48
Figure 02_image293
Figure 02_image295
Figure 02_image297
B 49 B 50 B 51
Figure 02_image299
Figure 02_image301
Figure 02_image303
B 52 B 53 B 54
Figure 02_image305
Figure 02_image307
Figure 02_image309
B 55 B 56 B 57
Figure 02_image311
Figure 02_image313
Figure 02_image315
B 58 B 59 B 60
Figure 02_image317
Figure 02_image319
Figure 02_image321
B 61 B 62 B 63
Figure 02_image323
Figure 02_image325
Figure 02_image327
B 64 B 65 B 66
Figure 02_image329
Figure 02_image331
Figure 02_image333
B 67 B 68 B 69
Figure 02_image335
Figure 02_image337
Figure 02_image339
B 70 B 71 B 72
Figure 02_image341
Figure 02_image343
Figure 02_image345
B 73 B 74 B 75
Figure 02_image347
Figure 02_image349
Figure 02_image351
B 76 B 77 B 78
Figure 02_image353
Figure 02_image355
Figure 02_image357
B 79 B 80 B 81
Figure 02_image359
Figure 02_image361
Figure 02_image363
B 82 B 83 B 84
Figure 02_image365
Figure 02_image367
Figure 02_image369
B 85 B 86 B 87
Figure 02_image371
Figure 02_image373
Figure 02_image375
B 88 B 89 B 90
Figure 02_image377
Figure 02_image379
Figure 02_image381
B 91 B 92 B 93
Figure 02_image383
Figure 02_image385
Figure 02_image387
B 94 B 95 B 96
Figure 02_image389
Figure 02_image391
Figure 02_image393
B 97 B 98 B 99
Figure 02_image395
Figure 02_image397
Figure 02_image399
B 100 B 101 B 102
Figure 02_image401
Figure 02_image403
Figure 02_image405
B 103 B 104 B 105
Figure 02_image407
Figure 02_image409
Figure 02_image411
B 106 B 107 B 108
Figure 02_image413
Figure 02_image415
Figure 02_image417
B 109 B 110 B 111
Figure 02_image419
Figure 02_image421
Figure 02_image423
B 112 B 113 B 114
Figure 02_image425
Figure 02_image427
Figure 02_image429
B 115 B 116 B 117
Figure 02_image431
Figure 02_image433
Figure 02_image435
B 118 B 119 B 120
Figure 02_image437
Figure 02_image439
Figure 02_image441
B 121 B 122 B 123
Figure 02_image443
Figure 02_image445
Figure 02_image447
B 124 B 125 B 126
Figure 02_image449
Figure 02_image451
Figure 02_image453
B 127 B 128 B 129
Figure 02_image455
Figure 02_image457
Figure 02_image459
B 130 B 131 B 132
Figure 02_image461
Figure 02_image463
Figure 02_image465
B 133 B 134 B 135
Figure 02_image467
Figure 02_image469
Figure 02_image471
B 136 B 137 B 138
Figure 02_image473
Figure 02_image475
Figure 02_image477
B 139 B 140 B 141
Figure 02_image479
Figure 02_image481
Figure 02_image483
B 142 B 143 B 144
Figure 02_image485
Figure 02_image487
Figure 02_image489
B 145 B 146 B 147
Figure 02_image491
Figure 02_image493
Figure 02_image495
B 148 B 149 B 150
Figure 02_image497
Figure 02_image499
Figure 02_image501
B 151 B 152 B 153
Figure 02_image503
Figure 02_image505
Figure 02_image507
B 154 B 155 B 156
Figure 02_image509
Figure 02_image511
Figure 02_image513
B 157 B 158 B 159
Figure 02_image515
Figure 02_image517
Figure 02_image519
B 160 B 161 B 162
Figure 02_image521
Figure 02_image523
Figure 02_image525
B 163 B 164 B 165
Figure 02_image527
Figure 02_image529
Figure 02_image531
B 166 B 167 B 168
Figure 02_image533
Figure 02_image535
Figure 02_image537
B 169 B 170 B 171
Figure 02_image539
Figure 02_image541
Figure 02_image543
B 172 B 173 B 174
Figure 02_image545
Figure 02_image547
Figure 02_image549
B 175 B 176 B 177
Figure 02_image551
Figure 02_image553
Figure 02_image555
B 178 B 179 B 180
Figure 02_image557
Figure 02_image559
Figure 02_image561
B 181 B 182 B 183
Figure 02_image563
Figure 02_image565
Figure 02_image567
B 184 B 185 B 186
Figure 02_image569
Figure 02_image571
Figure 02_image573
B 187 B 188 B 189
Figure 02_image575
Figure 02_image577
Figure 02_image579
B 190 B 191 B 192
Figure 02_image581
Figure 02_image583
Figure 02_image585
B 193 B 194 B 195
Figure 02_image587
Figure 02_image589
Figure 02_image591
B 196 B 197 B 198
Figure 02_image593
Figure 02_image595
Figure 02_image597
B 199 B 200 B 201
Figure 02_image599
Figure 02_image601
Figure 02_image603
B 202 B 203 B 204
Figure 02_image605
Figure 02_image607
Figure 02_image609
B 205 B 206 B 207
Figure 02_image611
Figure 02_image613
Figure 02_image615
B 208 B 209 B 210
Figure 02_image617
Figure 02_image619
Figure 02_image621
B 211 B 212 B 213
Figure 02_image623
Figure 02_image625
Figure 02_image627
B 214 B 215 B 216
Figure 02_image629
Figure 02_image631
Figure 02_image633
B 217 B 218 B 219
Figure 02_image635
Figure 02_image637
Figure 02_image639
B 220 B 221 B 222
Figure 02_image641
Figure 02_image643
Figure 02_image645
B 223 B 224 B 225
Figure 02_image647
Figure 02_image649
Figure 02_image651
B 226 B 227 B 228
Figure 02_image653
Figure 02_image655
Figure 02_image657
B 229 B 230 B 231
Figure 02_image659
Figure 02_image661
Figure 02_image663
B 232 B 233 B 234
Figure 02_image665
Figure 02_image667
Figure 02_image669
B 235 B 236 B 237
Figure 02_image671
Figure 02_image673
Figure 02_image675
B 238 B 239 B 240
Figure 02_image677
Figure 02_image679
Figure 02_image681
B 241 B 242 B 243
Figure 02_image683
Figure 02_image685
Figure 02_image687
B 244 B 245 B 246
Figure 02_image689
Figure 02_image691
Figure 02_image693
B 247 B 248 B 249
Figure 02_image695
Figure 02_image697
Figure 02_image699
B 250 B 251 B 252
Figure 02_image701
Figure 02_image703
Figure 02_image705
B 253 B 254 B 255
Figure 02_image707
Figure 02_image709
Figure 02_image711
B 256 B 257 B 258
Figure 02_image713
Figure 02_image715
Figure 02_image717
B 259 B 260 B 261
Figure 02_image719
Figure 02_image721
Figure 02_image723
B 262 B 263 B 264
Figure 02_image725
Figure 02_image727
Figure 02_image729
B 265 B 266 B 267
Figure 02_image731
Figure 02_image733
Figure 02_image735
B 268 B 269 B 270
Figure 02_image737
Figure 02_image739
Figure 02_image741
B 271 B 272 B 273
Figure 02_image743
Figure 02_image745
Figure 02_image747
B 274 B 275 B 276
Figure 02_image749
Figure 02_image751
Figure 02_image753
B 277 B 278 B 279
Figure 02_image755
Figure 02_image757
Figure 02_image759
B 280 B 281 B 282
Figure 02_image761
Figure 02_image763
Figure 02_image765
B 283 B 284 B 285
Figure 02_image767
Figure 02_image769
Figure 02_image771
B 286 B 287 B 288
Figure 02_image773
Figure 02_image775
Figure 02_image777
B 289 B 290 B 291
Figure 02_image779
Figure 02_image781
Figure 02_image783
B 292 B 293 B 294
Figure 02_image785
Figure 02_image787
Figure 02_image789
B 295 B 296 B 297
Figure 02_image791
Figure 02_image793
Figure 02_image795
B 298 B 299 B 300
Figure 02_image797
Figure 02_image799
Figure 02_image801
B 301 B 302 B 303
Figure 02_image803
Figure 02_image805
Figure 02_image807
B 304 B 305 B 306
Figure 02_image809
Figure 02_image811
Figure 02_image813
B 307 B 308 B 309
Figure 02_image815
Figure 02_image817
Figure 02_image819
B 310 B 311 B 312
Figure 02_image821
Figure 02_image823
Figure 02_image825
B 313 B 314 B 315
Figure 02_image827
Figure 02_image829
Figure 02_image831
B 316 B 317 B 318
Figure 02_image833
Figure 02_image835
Figure 02_image837
B 319 B 320 B 321
Figure 02_image839
Figure 02_image841
Figure 02_image843
B 322 B 323 B 324
Figure 02_image845
Figure 02_image847
Figure 02_image849
B 325 B 326 B 327
Figure 02_image851
Figure 02_image853
Figure 02_image855
B 328 B 329 B 330
Figure 02_image857
Figure 02_image859
Figure 02_image861
B 331 B 332 B 333
Figure 02_image863
Figure 02_image865
Figure 02_image867
B 334 B 335 B 336
Figure 02_image869
Figure 02_image871
Figure 02_image873
B 337 B 338 B 339
Figure 02_image875
Figure 02_image877
Figure 02_image879
B 340 B 341 B 342
Figure 02_image881
Figure 02_image883
Figure 02_image885
B 343 B 344 B 345
Figure 02_image887
Figure 02_image889
Figure 02_image891
B 346 B 347 B 348
Figure 02_image893
Figure 02_image895
Figure 02_image897
B 349 B 350 B 351
Figure 02_image899
Figure 02_image901
Figure 02_image903
B 352 B 353 B 354
Figure 02_image905
Figure 02_image907
Figure 02_image909
B 355 B 356 B 357
Figure 02_image911
Figure 02_image913
Figure 02_image915
B 358 B 359 B 360
Figure 02_image917
Figure 02_image919
Figure 02_image921
B 361 B 362  
Figure 02_image923
    
Figure 02_image925
  。		  
上述化合物在OLED器件中的應用。
所述應用為化合物作為OLED器件的電子傳輸層材料、空穴阻隔層材料和/或光提取層材料。
本發明的化合物材料具有昇華溫度低，光、電、熱穩定性好，發光效率高，電壓低、壽命長，折射率高、可見光區折射率差異小等優點，可用於有機發光器件中，特別是作為電子傳輸材料、空穴阻隔層材料、光提取層材料，該器件具有驅動電壓低、發光效率高、器件壽命長的優點，具有應用於AMOLED產業的可能。
下述實施例僅僅是為了便於理解技術發明，不應視為本發明的具體限制。
本發明中的化合物合成中涉及的原物料和溶劑等均購自於Alfa、Acros等本領域技術人員熟知的供應商。
實施例：
（1）化合物A1的合成：
Figure 02_image927
化合物03的合成：向一個2L單口瓶，依次將化合物01（53.17g，0.57mol，1.0eq）、化合物02（200g，0.57mol，1.0eq），NaHCO3（94.9g，1.14mol，2.0eq）、異丙醇（1000ml）投入到燒瓶中，油浴加熱到80度左右，保溫攪拌回流7h，取樣點板原料反應完。降溫，滴加去離子水，攪拌4h左右，抽濾。固體用乙醇打漿，抽濾烘乾。得到157g白色固體化合物03，收率79.6%。質譜：349.03（M+H）。
化合物04的合成：向一個1L單口瓶，依次加入化合物03（60g，171.81mmol，1.0eq）、雙聯頻呐硼酸酯（56.72g，223.35mmol，1.3eq）、Pd（dppf）Cl2（1.26g，1.72mmol，0.01eq）、CH3COOK（33.72g，343.62mmol，2.0eq），600ml二氧六環，攪拌下N2置換3次，加熱，回流3h。TLC監測反應完全（EA/Hex=1:8）。反應液降至室溫，真空濃縮二氧六環至無溶劑餾出，加入600mlDCM將固體溶解，用水200ml洗一次，將水相用200ml DCM提一次，合併有機相，並用水洗兩次（每次200ml），將有機相有無水MgSO4乾燥。過矽膠濾，並用DCM 300ml淋洗，濃縮有機相至僅剩150ml左右，加入正己烷500ml降至室溫結晶2h。過濾，濾餅用正己烷100ml，淋洗，抽乾得到59g，真空乾燥過夜，得到54g類白色固體化合物04，收率78.2%。質譜：397.30（M+H）。
化合物A1的合成：向一個1L單口瓶，依次加入化合物04（45.06g，113.73mmol，2.1eq）、化合物05（12.62g，54.16mmol，1.0eq），Pd132（383.5mg，0.5416mmol，0.01eq），K2 CO3 （15.69g，113.73mmol，2.1eq），甲苯450ml，乙醇150ml，水150ml攪拌下N2置換3次，加熱，回流20h。TLC監測反應完全，降至室溫後過濾，濾餅分別依次用水200ml，甲醇100ml，甲苯100ml，甲醇100ml淋洗，抽乾，得到灰白色固體37g。將所得固體用THF重結晶，得到28g白色固體化合物A1。得到的化合物經過昇華純化得到21克米白色固體化合物A1，收率75%。質譜：692.28（M+H）；1H NMR (400 MHz, CDCl3) δ 8.13 (d, J = 8.4 Hz, 4H), 7.98 (d, J = 6.9 Hz, 2H), 7.87 (s, 2H), 7.81 (d, J = 8.3 Hz, 4H), 7.72 (t, J = 8.4 Hz, 4H), 7.58 – 7.43 (m, 13H), 7.24 – 7.19 (m, 2H), 6.75 (t, J = 6.8 Hz, 2H)。
（2）化合物B283的合成：
Figure 02_image929
化合物08的合成：參照化合物A1合成過程中，化合物04的合成方式和處理方法，只需要將對應的原物料變更即可。質譜：397.30（M+H）。
化合物10的合成：將化合物08（22g，55.53mmol，2.1eq）、化合物09（22.5g，53.44mmol，1.04eq）、K2 CO3 （11g，79.71mmol，1.5eq）、Pd(PPh3 )4 （1.2g，1.04mmol，0.02eq）、甲苯（400ml）、乙醇（50ml）、水（50ml）依次加入到1L的四口燒瓶中，置換N2三次，升溫至80℃，攪拌6小時，TLC顯示反應完全。反應液降溫後，過濾，濾渣用乙醇/水打漿，抽濾得25g灰色固體化合物10，收率75%。質譜：612.19（M+H）。
化合物11的合成：將化合物10（25g，40.90mmol，1.0eq）、雙聯頻呐硼酸酯（15.5g，61mmol，1.5eq）、X-Phos（0.8g，1.68mmol，0.04eq）、CH3 COOK（8g，81.52mmol，2.0eq）、dioxane（400ml）、Pd(OAc)2 （183mg，0.81mmol，0.02eq）依次加入至1L的四口燒瓶中，置換N2三次，升溫至105℃，攪拌3小時，TLC顯示反應完全。反應液降溫後，加DCM（200ml），矽膠過濾，母液水洗後旋乾， 得到的殘渣用甲苯/正己烷重結晶得26g白色固體化合物11，收率91%。質譜：704.31（M+H）。
化合物B283的合成：將化合物11（26g，36.97mmol，1.0eq）、化合物12（10.3g，55.67mmol，1.5eq）、K2 CO3 （10.2g，73.91mmol，2.0eq）、Pd-132（0.5g，0.7061mmol，0.02eq）、甲苯（300ml）、乙醇（50ml）、水（50ml）依次加入至1L的四口燒瓶中，置換N2三次，開始升溫體系至85℃，攪拌5小時，反應完全。降溫後反應液加DCM稀釋（500ml），濾矽膠，母液水洗後旋乾得25g粗品，殘渣用Tol/hex重結晶得12g白色固體化合物B283，收率48%。得到的化合物經過昇華純化得到7.56克米白色固體化合物B283，收率63%。質譜：683.28（M+H）；1H NMR (400 MHz, CDCl3) δ 8.99 (s, 1H), 8.77-8.73 (m, 5H), 8.13-8.11 (d, 2H), 7.99-7.87 (m, 2H), 7.78-7.69 (m, 5H), 7.64 – 7.52 (m, 8H), 7.34 – 7.29 (t, 2H), 7.24 – 7.21 (t, 2H), 7.14 – 7.12 (d, 1H),2.64 (s, 3H) ,2.60 (s, 3H)。
（3）化合物A3的合成：
Figure 02_image931
化合物A3的合成：選取對應的材料，參照化合物A1的合成、昇華得到黃色固體化合物A3。
（4）化合物B19的合成：
Figure 02_image933
化合物B19的合成：選取對應的材料，參照化合物B283的合成、昇華得到米白色固體化合物B19。
（5）化合物B23的合成：
Figure 02_image935
化合物B23的合成：選取對應的材料，參照化合物B283的合成、昇華得到米白色固體化合物B23。
（6）化合物A46的合成：
Figure 02_image937
化合物A46的合成：選取對應的材料，參照化合物A1的合成、昇華得到黃色固體化合物A46。
（7）化合物A2的合成：
Figure 02_image939
化合物A2的合成：選取對應的材料，參照化合物A1的合成、昇華得到黃色固體化合物A2。
選取對應的材料，用同樣類似的方法可以用於合成、昇華得到其他化合物。
應用例：
（1）化合物性能對比：本發明的化合物在OLED器件中可作為光提取層材料，具有較高的玻璃化轉變溫度、較高的折射率、可見光區較小的折射率差值。基本性能列於下表1 表1：折射率對比：
  玻璃化溫度 折射率 折射率差值
@450nm @520nm @630nm ΔB-G ΔB-R ΔG-R
化合物A1 150 2.14 2.05 2.00 0.09 0.14 0.05
化合物B283 128 2.02 1.96 1.94 0.06 0.08 0.02
化合物A3 156 2.21 2.16 2.06 0.05 0.15 0.1
化合物B19 134 2.09 2.03 1.98 0.06 0.11 0.05
化合物B23 133 2.06 1.99 1.94 0.07 0.12 0.05
化合物A46 158 2.03 1.95 1.91 0.08 0.12 0.04
化合物A2 155 2.24 2.12 2.06 0.12 0.18 0.06
HTM1 134 1.99 1.91 1.85 0.08 0.14 0.06
對比化合物3 132 1.99 1.89 1.84 0.1 0.15 0.05
（2）有機電致發光器件的製作 將50mm*50mm*1.0mm的具有ITO（100nm）透明電極的玻璃基板在乙醇中超聲清洗10分鐘，再150度烘乾後經過N2 Plasma處理30分鐘。將洗滌後的玻璃基板安裝在真空蒸鍍裝置的基板支架上，首先在有透明電極線一側的面上按照覆蓋透明電極的方式蒸鍍化合物HATCN，形成膜厚為5nm的薄膜，緊接著蒸鍍一層HTM1形成膜厚為60nm的薄膜，再在HTM1薄膜上蒸鍍一層HTM2形成膜厚為10nm的薄膜，然後，在HTM2膜層上再採用共蒸鍍的模式蒸鍍主體材料CBP和摻雜材料，膜厚為30nm，主體材料和摻雜材料比例為90%：10%。在發光層上再依次按照下表的搭配蒸鍍HBL（5nm）作為空穴阻隔層材料、ETL（30nm）作為電子傳輸材料，接著在電子傳輸材料層之上蒸鍍LiF(1nm) 作為電子注入材料，接著再採用共蒸鍍的模式蒸鍍Mg/Ag（18nm,1:9）作為陰極材料,最後在陰極材料之上按照下表的搭配蒸鍍CPL（50nm）作為光提取層材料。
Figure 02_image941
器件性能評價 將上述器件進行器件性能測試，在各實施例和比較例中，使用恒定電流電源（Keithley 2400），使用固定的電流密度流過發光元件，使用分光輻射倆都系（CS 2000）測試發光波譜。同時測定電壓值以及測試亮度為初始亮度的90%的時間（LT90）。結果如下表2： 表2：
  HBL ETL CPL 啟動電壓V @3000nits 電流效率Cd/A @3000nits LT90@ 3000nits
實施例1 化合物A1 化合物A1 HTM1 4.6 61 186
實施例2 化合物B283 化合物B283 HTM1 4.5 63 175
實施例3 化合物A3 化合物A3 HTM1 4.6 64 192
實施例4 化合物B19 化合物B19 HTM1 4.4 62 169
實施例5 化合物B23 化合物B23 HTM1 4.3 63 173
實施例6 化合物A46 化合物A46 HTM1 4.5 61 181
實施例7 化合物A2 化合物A2 HTM1 4.5 60 156
實施例8 化合物B340 化合物B283 化合物A3 4.2 68 216
實施例9 對比化合物1 對比化合物1 化合物A3 4.7 53 96
實施例10 對比化合物2 對比化合物2 化合物A3 4.7 55 130
實施例11 化合物B340 化合物B23 化合物A3 4.6 69 256
實施例12 化合物B340 化合物B9 化合物A2 4.7 67 234
對比例1 對比化合物1 對比化合物1 HTM1 5.2 48 92
對比例2 對比化合物2 對比化合物2 HTM1 4.9 50 125
由上面表格中的資料對比可知，使用本發明的化合物應用於有機電致發光器件作為空穴阻隔層或電子傳輸層或光提取層材料，相較於對比化合物在驅動電壓、發光效率、器件壽命都表現出更加優越的性能。
上述結果表明本發明的化合物具有昇華溫度低，光、電、熱穩定性好，折射率高、可見光區折射率差異小等優點，該化合物製備的器件具有電壓低、壽命長，發光效率高等優點，可用於有機發光器件中。特別是作為電子傳輸材料、空穴阻隔層材料、光提取層材料，具有應用於AMOLED產業的可能。
Figure 109109688-A0101-11-0002-3

Claims (14)

  1. 一種化合物，其結構式如式(I)所示：
    Figure 109109688-A0305-02-0042-1
     其中，R1為單鍵、烷基、雜烷基、環烷基、取代或未取代的C6-C30的非稠環芳基、取代或未取代的C3-C27的非稠環雜芳基；其中，R2、R3、R4獨立的選自氫、氘、鹵素、烷基、雜烷基、環烷基、烷氧基、芳氧基、氨基、矽烷基、腈、異腈、膦基、取代或未取代的C6-C60的芳基、取代或未取代的C1-C60的雜芳基、經取代或未經取代的單環或多環C3-C60脂肪族環或芳香族環且R3、R4中至少有一個為取代或未取代的C6-C60的芳基、取代或未取代的C1-C60的雜芳基、經取代或未經取代的單環或多環C3-C60脂肪族環或芳香族環，其中雜烷基或雜芳基中的一個或多個碳原子可由選自O、S、N、Se、Si、Ge中的至少一個雜原子替換；所述取代為被氘、鹵素、C1-C30烷基、C1-C30雜烷基、C3-C30環烷基、氨基、矽烷基、腈、異腈、、膦基、C6-C60的芳基、C1-C60的雜芳基取代；其中，X1、X2、X3獨立的表示為CH或者N；X4、X5、X6獨立的表示為CR0或者N，R0獨立的選自氫、氘、鹵素、烷基、雜烷基、芳烷基、烷氧基、芳氧基、氨基、矽烷基、芳基、雜芳基、腈、異腈、膦基，且相鄰的R0能鍵接成並環；當X1、X2、X3表示為CH時，R4不為取代或未取代的咪唑基。
  2. 如請求項1所述的化合物，其中，R1為單鍵、C1-C30烷基、C1-C30雜烷基、C3-C30環烷基、取代或未取代的C6-C30的非稠環芳基、取代或未取代的C3-C27的非稠環雜芳基；其中，R2、R3、R4獨立的選自氫、氘、鹵素、C1-C30烷基、C1-C30雜烷基、C3-C30環烷基、氨基、矽烷基、腈、異腈、膦基、取代或未取代的C6-C60的芳基、取代或未取代的C1-C60的雜芳基、經取代或未經取代的單環或多環C3-C60脂肪族環或芳香族環且R3、R4中至少有一個為取代或未取代的C6-C60的芳基、取代或未取代的C1-C60的雜芳基、經取代或未經取代的單環或多環C3-C60脂肪族環或芳香族環，其中雜烷基或雜芳基中的一個或多個碳原子由選自O、S、N中的至少一個雜原子替換；所述取代為被氘、鹵素、C1-C30烷基、C1-C30雜烷基、C3-C30環烷基、氨基、矽烷基、腈、異腈、、膦基、C6-C60的芳基、C1-C60的雜芳基取代；其中，X1、X2、X3獨立的表示為CH或者N；X4、X5、X6獨立的表示為CR0或者N，R0獨立的選自氫、氘、鹵素、C1-C30烷基、C1-C30雜烷基、芳烷基、氨基、矽烷基、芳基、雜芳基、腈、異腈、膦基，且相鄰的R0能鍵接成並環。
  3. 如請求項1或2中任一項所述的化合物，其中，X1、X2、X3至少一個是N。
  4. 如請求項3所述的化合物，其中，R3或R4至少之一含有以下結構式(II)，其中，R1為單鍵、烷基、雜烷基、環烷基、C1-C30烷基取代或未取代的C6-C30的非稠環芳基、C1-C30烷基取代或未取代的C3-C27的非稠環雜 芳基；其中，R2為氫、氘、鹵素、烷基、雜烷基、環烷基、C1-C30烷基取代或未取代的C6-C60的芳基、C1-C30烷基取代或未取代的C1-C60的雜芳基
    Figure 109109688-A0305-02-0044-2
  5. 如請求項4所述的化合物，其中，R3、R4中一個為式(II)結構，另一個為C1-C4烷基取代或未取代的C6-C18的芳基、C1-C4烷基取代或未取代的C3-C15的雜芳基；R1為C1-C4烷基取代或未取代的C6-C18的非稠環芳基、C1-C4烷基取代或未取代的C3-C15的非稠環雜芳基；R2為C1-C4烷基取代或未取代的C6-C18的芳基、C1-C4烷基取代或未取代的C3-C15的雜芳基。
  6. 如請求項5所述的化合物，其中，R1為C6-C18的非稠環芳基或C5-C15的非稠環雜芳基；R2為C6-C18的芳基或C5-C15的雜芳基。
  7. 如請求項6所述的化合物，為下列化合物之一：
    Figure 109109688-A0305-02-0044-3
    Figure 109109688-A0305-02-0045-4
    Figure 109109688-A0305-02-0046-5
    Figure 109109688-A0305-02-0047-6
    Figure 109109688-A0305-02-0048-7
    Figure 109109688-A0305-02-0049-8
    Figure 109109688-A0305-02-0050-9
  8. 請求項1至2中任一項所述的化合物，其中，X1、X2、X3表示為CH。
  9. 如請求項8所述的化合物，其中，R1為單鍵、C1-C30烷基取代或未取代的C6-C30的非稠環芳基、C1-C30烷基取代或未取代的C3-C27的非稠環雜芳基；其中，R2為C1-C30烷基取代或未取代的C6-C60的芳基、C1-C30烷基取代或未取代的C1-C60的雜芳基；R3、R4為氫、氘、鹵素、烷基、雜烷基、環烷基、C1-C30烷基取代或未取代的C6-C60的芳基、C1-C30烷基取代或未取代的C1-C60的雜芳基、經取代或未經取代的單環或多環C3-C60脂肪族環或芳香族環且R3、R4中至少有一個為C1-C30烷基取代或未取代的C6-C60的芳基、C1-C30烷基取代或未取代的C1-C60的雜芳基、經取代或未經取代的單環或多環C3-C60脂肪族環或芳香族環，且R4不為取代或未取代的咪唑基。
  10. 如請求項9所述的化合物，其中，R1為單鍵、C1-C4烷基取代或未取代的C6-C18的非稠環芳基、C1-C4烷基取代或未取代的C3-C15的非稠環雜芳基；R2為C1-C4烷基取代或未取代的C6-C18的芳基、C1-C4烷基取代或未取代的C3-C15的雜芳基；R3、R4為氫、氘、鹵素、烷基、C1-C4烷基取代或未取代的C6-C18的芳基、C1-C4烷基取代或未取代的C3-C15的雜芳基、經取代或未經取代的單環或多環C3-C18脂肪族環或芳香族環且R3、R4不同，且R4不為取代或未取代的咪唑基。
  11. 如請求項10所述的化合物，其中，R1為單鍵、C6-C18的非稠環芳基或C3-C15的非稠環雜芳基；R2為C6-C18的芳基或C3-C15的雜芳基。
  12. 如請求項11所述的化合物，為下列化合物之一：
    Figure 109109688-A0305-02-0051-10
    Figure 109109688-A0305-02-0052-11
    Figure 109109688-A0305-02-0053-12
    Figure 109109688-A0305-02-0054-13
    Figure 109109688-A0305-02-0055-14
    Figure 109109688-A0305-02-0056-15
    Figure 109109688-A0305-02-0057-16
    Figure 109109688-A0305-02-0058-17
    Figure 109109688-A0305-02-0059-18
    Figure 109109688-A0305-02-0060-20
    Figure 109109688-A0305-02-0061-22
    Figure 109109688-A0305-02-0062-24
    Figure 109109688-A0305-02-0063-25
    Figure 109109688-A0305-02-0064-27
    Figure 109109688-A0305-02-0065-28
    Figure 109109688-A0305-02-0066-30
    Figure 109109688-A0305-02-0067-32
    Figure 109109688-A0305-02-0068-34
    Figure 109109688-A0305-02-0069-35
    Figure 109109688-A0305-02-0070-36
  13. 一種如請求項1至12中任一項所述的化合物在OLED器件中的應用。
  14. 如請求項13所述的應用，其特徵在於作為OLED器件的電子傳輸層材料、空穴阻隔層材料和/或光提取層材料。
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