CN117003784B

CN117003784B - Boron-nitrogen-containing polycyclic aromatic hydrocarbon based on five-membered heterocyclic structure, preparation method and organic electroluminescent device

Info

Publication number: CN117003784B
Application number: CN202311276923.5A
Authority: CN
Inventors: 李成龙; 王悦
Original assignee: Jilin University
Current assignee: Jilin University
Priority date: 2023-10-07
Filing date: 2023-10-07
Publication date: 2024-01-05
Anticipated expiration: 2043-10-07
Also published as: CN117003784A

Abstract

The invention relates to boron-nitrogen-containing polycyclic aromatic hydrocarbon based on a five-membered heterocyclic structure, a preparation method and an organic electroluminescent device, and belongs to the technical field of organic photoelectric functional materials. Solves the technical problem that the commercialization process of the MR-TADF material with the B/N molecular system as the core structure in the prior art is hindered by the serious efficiency roll-off phenomenon. The boron-nitrogen-containing polycyclic aromatic hydrocarbon organic photoelectric functional material based on the five-membered heterocyclic ring structure is a brand new MR-TADF material with a molecular skeleton central ring being a non-benzene aromatic ring with the five-membered heterocyclic ring structure, greatly enriches an MR-TADF material system, enhances the SOC and reduces delta E due to the introduction of asymmetric rings (such as furan and thiophene rings) at the molecular skeleton center of the material _ST The roll-off (roll-off) of the efficiency is obviously reduced, and further, the higher photoelectric conversion efficiency of the OLED device is realized.

Description

Boron-nitrogen-containing polycyclic aromatic hydrocarbon based on five-membered heterocyclic structure, preparation method and organic electroluminescent device

Technical Field

The invention belongs to the technical field of organic photoelectric functional materials, and particularly relates to boron-nitrogen-containing polycyclic aromatic hydrocarbon based on a five-membered heterocyclic structure, a preparation method and an organic electroluminescent device.

Background

Since 2016, by introducing electron-deficient centers (such as boron atoms) and electron-rich centers (such as nitrogen atoms) having opposite resonance effects based on a polycyclic aromatic hydrocarbon skeleton, the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO) were induced to be localized on different atoms in the molecular skeleton, respectively, thereby obtaining a polymer having a small singlet-triplet energy level difference (. DELTA.E _ST ) And multiple resonance thermally activated delayed fluorescence (multi-resonance thermally activated delayed fluorescence, MR-TADF) materials of narrow spectral properties. Such materials have a narrow luminescence spectrum, high fluorescence efficiency, and a small ΔE _ST Thus(s)Is receiving extensive attention.

Although MR-TADF materials with a B/N molecular system as a core structure have achieved higher External Quantum Efficiency (EQE) and narrower full width at half maximum (FWHM), at high currents, the efficiency decreases due to collisions between triplet states of the luminescent guest of the material, and this serious roll-off phenomenon hinders the commercialization of MR-TADF materials. By enhancing spin-orbit coupling (SOC) of molecules and reducing ΔE _ST Thereby increasing the inter-reverse-train crossing rate k _RISC The roll-off can be effectively reduced, and the device efficiency under high brightness is improved.

Disclosure of Invention

The invention mainly solves the technical problem that the commercialization process of an MR-TADF material taking a B/N molecular system as a core structure in the prior art is hindered by serious efficiency roll-off phenomenon, and provides a boron-nitrogen-containing polycyclic aromatic hydrocarbon based on a five-membered heterocyclic structure, a preparation method and an organic electroluminescent device. The material is a brand new MR-TADF material with a five-membered heterocyclic ring structure as the central ring of the molecular skeleton and a non-benzene aromatic ring, and the introduction of the asymmetric five-membered heterocyclic ring at the molecular skeleton of the material leads to the enhancement of the intramolecular charge transfer state, thereby being beneficial to reducing delta E _ST . Meanwhile, due to the introduction of hetero atoms, the SOC can be enhanced, so that the efficiency roll-off is obviously reduced, and the high device efficiency of the OLED device under high brightness is realized.

In order to solve the technical problems, the technical scheme of the invention is as follows:

a boron-nitrogen-containing polycyclic aromatic hydrocarbon based on five-membered heterocyclic ring structure has the following structural general formula:

；

1 (1)

Wherein X is a direct bond, O, S, se, te, NR ₆ 、C(R ₇ )(R ₈ )、Si(R ₇ )(R ₈ )、Ge(R ₇ )(R ₈ ) One of the following;

y is O, S, se, NR ₉ One of the following；

The rings CY1, CY2, CY3 and CY4 are the same or different and are each independently a single ring group or a condensed ring group of C5-C30 or are each independently a single heterocyclic group or a condensed heterocyclic group of C5-C30, wherein hetero atoms are one or more of N, O, S, si;

R ₁ 、R ₂ 、R ₃ 、R ₄ 、R ₅ 、R ₆ 、R ₇ 、R ₈ And R is ₉ The same or different are each independently selected from hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxy, mercapto, cyano, nitro, amidino, nitrile, hydrazone, carboxylic acid, carboxylate, sulfonic acid, sulfonate, phosphate, unsubstituted or R ₁₁ Substituted C1-C10 alkyl, unsubstituted or R ₁₁ Substituted C2-C10 alkenyl, unsubstituted or R ₁₁ Substituted C2-C10 alkynyl, unsubstituted or R ₁₁ Substituted C1-C10 alkoxy, unsubstituted or R ₁₁ Substituted C1-C10 alkylthio, unsubstituted or R ₁₁ Substituted C3-C10 cycloalkyl, unsubstituted or R ₁₁ Substituted C1-C10 heterocycloalkyl, unsubstituted or R ₁₁ Substituted C3-C10 cycloalkenyl, unsubstituted or R ₁₁ Substituted C2-C10 heterocycloalkenyl, unsubstituted or R ₁₁ Substituted C6-C30 aryl, unsubstituted or R ₁₁ Substituted C7-C30 aralkyl, unsubstituted or R ₁₁ Substituted C6-C30 aryloxy, unsubstituted or R ₁₁ Substituted C6-C30 arylthio, unsubstituted or R ₁₁ Substituted C3-C30 heteroaryl, unsubstituted or R ₁₁ Substituted C4-C30 heteroaralkyl, unsubstituted or R ₁₁ Substituted C3-C30 heteroaryloxy, unsubstituted or R ₁₁ Substituted C3-C30 heteroarylthio, -N (Q) ₁ )(Q ₂ )、-Si(Q ₃ )(Q ₄ )(Q ₅ )、-B(Q ₆ )(Q ₇ ) or-P (=O) (Q ₈ )(Q ₉ ) Wherein the heteroatom is one or more of N, O, S, si;

n ₁ -n ₄ each independently is an integer of 1 or more;

Substituent R ₁₁ Identical or different, selected from hydrogen, deuterium, -F, -Cl, -Br, -I, -CD ₃ 、-CD ₂ H、-CDH ₂ 、-CF ₃ 、-CF ₂ H、-CFH ₂ Hydroxyl, mercapto, cyano, nitro, amidino, nitrile, hydrazone, carboxylic acid, carboxylate, sulfonic acid, sulfonate, phosphate, unsubstituted or R ₂₁ Substituted C1-C10 alkyl, unsubstituted or R ₂₁ Substituted C2-C10 alkenyl, unsubstituted or R ₂₁ Substituted C2-C10 alkynyl, unsubstituted or R ₂₁ Substituted C1-C10 alkoxy, unsubstituted or R ₂₁ Substituted C1-C10 alkylthio, unsubstituted or R ₂₁ Substituted C3-C10 cycloalkyl, unsubstituted or R ₂₁ Substituted C2-C10 heterocycloalkyl, unsubstituted or R ₂₁ Substituted C3-C10 cycloalkenyl, unsubstituted or R ₂₁ Substituted C2-C10 heterocycloalkenyl, unsubstituted or R ₂₁ Substituted C6-C30 aryl, unsubstituted or R ₂₁ Substituted C7-C30 aralkyl, unsubstituted or R ₂₁ Substituted C6-C30 aryloxy, unsubstituted or R ₂₁ Substituted C6-C30 arylthio, unsubstituted or R ₂₁ Substituted C3-C30 heteroaryl, unsubstituted or R ₂₁ Substituted C4-C30 heteroaralkyl, unsubstituted or R ₂₁ Substituted C3-C30 heteroaryloxy, unsubstituted or R ₂₁ Substituted C3-C30 heteroarylthio, -N (Q) ₁₁ )(Q ₁₂ )、-Si(Q ₁₃ )(Q ₁₄ )(Q ₁₅ )、-B(Q ₁₆ )(Q ₁₇ ) or-P (=O) (Q ₁₈ )(Q ₁₉ ) Wherein the heteroatom is one or more of N, O, S; or two adjacent substituents are bonded to form a ring;

Substituent R ₂₁ Identical or different, selected from hydrogen, deuterium, -F, -Cl, -Br, -I, -CD ₃ 、-CD ₂ H、-CDH ₂ 、-CF ₃ 、-CF ₂ H、-CFH ₂ Hydroxyl, mercapto, cyano, nitro, amidino, nitrile, hydrazone, carboxylic acid, carboxylate, sulfonic acid, sulfonate, phosphate, C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl, C1-C10 alkoxy, C1-C10 alkylthio, C3-C10 cycloalkyl, C2-C10 heterocycloalkyl, C3-C10 cycloalkenyl, C2-C10 heterocycloalkenyl, C6-C30 aryl, C7-C30 aralkyl, C6-C30 aryloxy,C6-C30 arylthio, C3-C30 heteroaryl, C3-C30 heteroaryloxy, C3-C30 heteroarylthio, C4-C30 heteroarylalkyl, wherein the heteroatom is one or more of N, O, S; or two adjacent substituents are bonded to form a ring;

wherein Q is ₁ -Q ₉ 、Q ₁₁ -Q ₁₉ Identical or different, each independently selected from hydrogen, deuterium, C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl, C1-C10 alkoxy, C1-C10 alkylthio, C3-C10 cycloalkyl, C2-C10 heterocycloalkyl, C3-C10 cycloalkenyl, C2-C10 heterocycloalkenyl, R ₁₁ Substituted or unsubstituted C6-C30 aryl, R ₁₁ Substituted or unsubstituted C7-C30 aralkyl, R ₁₁ Substituted or unsubstituted C6-C30 aryloxy, R ₁₁ Substituted or unsubstituted C6-C30 arylthio, R ₁₁ Substituted or unsubstituted C3-C30 heteroaryl, R ₁₁ Substituted or unsubstituted C4-C30 heteroaralkyl, R ₁₁ Substituted or unsubstituted C3-C30 heteroaryloxy, R ₁₁ A substituted or unsubstituted C3-C30 heteroarylthio group, wherein the heteroatom is one or more of N, O, S; or substituents attached to the same atom are bonded to form a ring.

Further:

x is preferably selected from direct bond, O, S, se, NR ₆ 、C(R ₇ )(R ₈ ) One of the following; y is one of O, S;

the rings CY1, CY2, CY3, and CY4, which are the same or different, are each independently preferably a C6-C30 monoaromatic or fused aromatic ring, or are each independently a C5-C30 monoaromatic or fused heteroaromatic ring, wherein the heteroatoms are one or more of N, O, S;

R ₁ 、R ₂ 、R ₃ 、R ₄ 、R ₅ 、R ₆ 、R ₇ and R is ₈ The radicals are identical or different and are each independently preferably selected from hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxy, mercapto, cyano, nitro, unsubstituted or R ₁₁ Substituted C1-C10 alkyl, unsubstituted or R ₁₁ Substituted C3-C10 cycloalkyl, unsubstituted or R ₁₁ Substituted C6-C30 aryl, unsubstituted or R ₁₁ Substituted C7-C30 aralkyl, unsubstituted or R ₁₁ Substituted C6-C30 aryloxy, unsubstituted or R ₁₁ Substituted C3-C30 heteroaryl, unsubstituted or R ₁₁ Substituted C4-C30 heteroaralkyl, unsubstituted or R ₁₁ Substituted C3-C30 heteroaryloxy, -N (Q) ₁ )(Q ₂ )、-Si(Q ₃ )(Q ₄ )(Q ₅ ) or-B (Q) ₆ )(Q ₇ ) Wherein the heteroatom is one or more of N, O, S;

n ₁ -n ₄ each independently is an integer from 1 to 6;

substituent R ₁₁ Identical or different, preferably from hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxy, mercapto, cyano, nitro, unsubstituted or R ₂₁ Substituted C1-C10 alkyl, unsubstituted or R ₂₁ Substituted C3-C10 cycloalkyl, unsubstituted or R ₂₁ Substituted C6-C30 aryl, unsubstituted or R ₂₁ Substituted C7-C30 aralkyl, unsubstituted or R ₂₁ Substituted C6-C30 aryloxy, unsubstituted or R ₂₁ Substituted C3-C30 heteroaryl, unsubstituted or R ₂₁ Substituted C4-C30 heteroaralkyl, unsubstituted or R ₂₁ Substituted C3-C30 heteroaryloxy, -N (Q) ₁₁ )(Q ₁₂ )、-Si(Q ₁₃ )(Q ₁₄ )(Q ₁₅ ) or-B (Q) ₁₆ )(Q ₁₇ ) Wherein the heteroatom is one or more of N, O, S; or two adjacent substituents are bonded to form a ring;

substituent R ₂₁ Identical or different, preferably from hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxy, mercapto, cyano, nitro, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C30 aryl, C7-C30 aralkyl, C6-C30 aryloxy, C3-C30 heteroaryl, C4-C30 heteroaralkyl, C3-C30 heteroaryloxy, wherein the heteroatom is one or more of N, O, S; or two adjacent substituents are bonded to form a ring;

Wherein Q is ₁ -Q ₇ 、Q ₁₁ -Q ₁₇ The radicals are identical or different and are each independently preferably selected from hydrogen, deuterium, C1-C10 alkyl, C3-C10 cycloalkyl, unsubstituted or R ₁₁ Substituted C6-C30 aryl, unsubstituted or R ₁₁ Substituted C7-C30 aralkyl, unsubstituted or R ₁₁ Substituted C6-C30 aryloxy, unsubstituted or R ₁₁ Substituted C3-C30 heteroaryl, unsubstituted or R ₁₁ Substituted C4-C30 heteroaralkyl, unsubstituted or R ₁₁ Substituted C3-C30 heteroaryloxy wherein the heteroatom is one or more of N, O, S; or substituents attached to the same atom are bonded to form a ring.

Still further:

the rings CY1, CY2, CY3 and CY4 are identical or different, preferably a C6-C20 monoaromatic or fused aromatic ring, or preferably a C5-C20 monoaromatic or fused heteroaromatic ring, wherein the heteroatom is one of N, O, S;

R ₁ 、R ₂ 、R ₃ 、R ₄ 、R ₅ 、R ₆ 、R ₇ and R is ₈ The radicals are identical or different and are each independently preferably selected from hydrogen, hydroxy, mercapto, unsubstituted or R ₁₁ Substituted C1-C4 alkyl, unsubstituted or R ₁₁ Substituted C6-C20 aryl, unsubstituted or R ₁₁ Substituted C7-C20 aralkyl, unsubstituted or R ₁₁ Substituted C6-C20 aryloxy, unsubstituted or R ₁₁ Substituted C3-C20 heteroaryl, unsubstituted or R ₁₁ Substituted C4-C20 heteroaralkyl, unsubstituted or R ₁₁ Substituted C3-C20 heteroaryloxy, -N (Q) ₁ )(Q ₂ )、-Si(Q ₃ )(Q ₄ )(Q ₅ ) or-B (Q) ₆ )(Q ₇ ) Wherein the heteroatom is one or more of N, O, S; or two adjacent substituents are bonded to form a ring;

substituent R ₁₁ Identical or different, preferably from hydrogen, hydroxy, mercapto, unsubstituted or R ₂₁ Substituted C1-C4 alkyl, unsubstituted or R ₂₁ Substituted C6-C20 aryl, unsubstituted or R ₂₁ Substituted C7-C20 aralkyl, unsubstituted or R ₂₁ Substituted C6-C20 aryloxy, unsubstituted or R ₂₁ Substituted C3-C20 heteroaryl, unsubstituted or R ₂₁ Substituted C4-C20 heteroaralkyl, unsubstituted or R ₂₁ Substituted C3-C20 heteroaryloxy, -N (Q) ₁₁ )(Q ₁₂ )、-Si(Q ₁₃ )(Q ₁₄ )(Q ₁₅ ) or-B (Q) ₁₆ )(Q ₁₇ ) Wherein the heteroatom is one or more of N, O, S; or two ofBonding between adjacent substituents to form a ring;

substituent R ₂₁ The same or different, further preferred is selected from hydrogen, methyl, isopropyl, tert-butyl, C6-C20 aryl, C7-C20 aralkyl, C6-C20 aryloxy, C3-C20 heteroaryl, C4-C20 heteroaralkyl, C3-C20 heteroaryloxy, wherein the heteroatom is one or more of N, O, S; or two adjacent substituents are bonded to form a ring;

wherein Q is ₁ -Q ₇ 、Q ₁₁ -Q ₁₇ The radicals are identical or different and are each independently preferably selected from hydrogen, C1-C4-alkyl, unsubstituted or R ₁₁ Substituted C6-C20 aryl, unsubstituted or R ₁₁ Substituted C7-C20 aralkyl, unsubstituted or R ₁₁ Substituted C6-C20 aryloxy, unsubstituted or R ₁₁ Substituted C3-C20 heteroaryl, unsubstituted or R ₁₁ Substituted C4-C20 heteroaralkyl, unsubstituted or R ₁₁ Substituted C3-C20 heteroaryloxy wherein the heteroatom is one or more of N, O, S; or substituents attached to the same atom are bonded to form a ring.

Further, the boron-nitrogen-containing polycyclic aromatic hydrocarbon based on the five-membered heterocyclic ring structure is shown in any one of the following structures:

1-1 1-2 1-3 1-4 1-5

1-6 1-7 1-8 1-9 1-10

1-11 1-12 1-13 1-14 1-15

1-16 1-17 1-18 1-19 1-20

1-21 1-22 1-23 1-24 1-25

1-26 1-27 1-28 1-29 1-30

wherein X is a direct bond (when X is a direct bond, the ring containing N is a five-membered ring), O, S, se,(representing bonding with two benzene rings), Y is O or S, R ₅ H, & gt>、/>、/>、/>Or->。

Still further, the boron-nitrogen-containing polycyclic aromatic hydrocarbon based on the five-membered heterocyclic ring structure is one of the following structural formulas:

compound 1 compound 2 compound 3 compound 4 compound 5

Compound 6 compound 7 compound 8 compound 9 compound 10

Compound 11 compound 12 compound 13 compound 14 compound 15

Compound 16 compound 17 compound 18 compound 19 compound 20

Compound 21 compound 22 compound 23 compound 24 compound 25

Compound 26 compound 27 compound 28 compound 29 compound 30

；

Compound 31 compound 32 compound 33 compound 34

；

Compound 35 compound 36 compound 37 compound 38

Compound 39 compound 40 compound 41 compound 42 compound 43

Compound 44 compound 45 compound 46 compound 47 compound 48

Compound 49 compound 50 compound 51 compound 52 compound 53

Compound 54 compound 55 compound 56 compound 57 compound 58

Compound 59 compound 60 compound 61 compound 62

Compound 63 compound 64 compound 65 compound 66

Compound 67 compound 68 compound 69 compound 70 compound 71

Compound 72 compound 73 compound 74 compound 75 compound 76

Compound 77 compound 78 compound 79 compound 80 compound 81

Compound 82 compound 83 compound 84 compound 85 compound 86

Compound 87 compound 88 compound 89 compound 90 compound 91

Compound 92 compound 93 compound 94 compound 95 compound 96

Compound 97 compound 98 compound 99 compound 100 compound 101

Compound 102 compound 103 compound 104 compound 105 compound 106

Compound 107 compound 108 compound 109 compound 110 compound 111

Compound 112 compound 113 compound 114 compound 115 compound 116

Compound 117 compound 118 compound 119 compound 120 compound 121

Compound 122 compound 123 compound 124 compound 125 compound 126

Compound 127 compound 128 compound 129 compound 130 compound 131

Compound 132 compound 133 compound 134 compound 135 compound 136

Compound 137 compound 138 compound 139 compound 140 compound 141

；

Compound 142 compound 143

Compound 144 compound 145 compound 146 compound 147 compound 148

Compound 149 compound 150 compound 151 compound 152 compound 153

Compound 154 compound 155 compound 156 compound 157 compound 158

Compound 159 compound 160 compound 161 compound 162 compound 163

Compound 164 compound 165 compound 166 compound 167 compound 168

；

Compound 169 compound 170 compound 171 compound 172 compound 173

Compound 174 compound 175 compound 176 compound 177 compound 178

Compound 179 compound 180 compound 181 compound 182 compound 183

Compound 184 compound 185 compound 186 compound 187 compound 188

Compound 189 compound 190 compound 191 compound 192 compound 193

Compound 194 compound 195 compound 196 compound 197 compound 198

Compound 199 compound 200 compound 201 compound 202 compound 203

Compound 204 compound 205 compound 206 compound 207 compound 208

Compound 209 compound 210 compound 211 compound 212 compound 213

Compound 214 compound 215 compound 216 compound 217 compound 218

Compound 219 compound 220 compound 221 compound 222 compound 223

Compound 224 compound 225 compound 226 compound 227 compound 228

Compound 229 compound 230 compound 231 compound 232 compound 233

Compound 234 compound 235 compound 236 compound 237 compound 238

；

Compound 239 compound 240 compound 241 compound 242 compound 243

；

Compound 244 compound 245 compound 246 compound 247 compound 248

；

Compound 249 compound 250 compound 251 compound 252 compound 253

；

Compound 254 compound 255 compound 256 compound 257 compound 258

；

Compound 259 compound 260 compound 261 compound 262 compound 263

；

Compound 264 compound 265 compound 266 compound 267 compound 268

；

Compound 269 compound 270 compound 271 compound 272 compound 273

；

Compound 274 Compound 275 Compound 276 compound 277 compound 278

；/>

Compound 279 compound 280 compound 281 compound 282 compound 283

Compound 284 compound 285 compound 286 compound 287 compound 288

Compound 289 compound 290 compound 291 compound 292 compound 293

Compound 294 compound 295 compound 296 compound 297 compound 298

Compound 299 compound 300 compound 301 compound 302 compound 303

Compound 304 compound 305 compound 306 compound 307 compound 308

Compound 309 compound 310 compound 311 compound 312 compound 313

Compound 314 compound 315 compound 316 compound 317 compound 318

Compound 319 compound 320 compound 321 compound 322 compound 323

Compound 324 compound 325 compound 326 compound 327 compound 328

Compound 329 compound 330 compound 331 compound 332 compound 333

Compound 334 compound 335 compound 336 compound 337 compound 338

Compound 339 compound 340 compound 341 compound 342 compound 343

Compound 344 compound 345 compound 346 compound 347 compound 348

Compound 349 compound 350 compound 351 compound 352 compound 353

Compound 354 compound 355 compound 356 compound 357 compound 358

Compound 359 compound 360 compound 361 compound 362 compound 363

；

Compound 364 compound 365 compound 366 compound 367 compound 368

；

Compound 369 compound 370 compound 371 compound 372 compound 373

；

Compound 374 compound 375 compound 376 compound 377 compound 378

；

Compound 379 compound 380 compound 381 compound 382 compound 383

；

Compound 384 compound 385 compound 386 compound 387 compound 388

；

Compound 389 compound 390 compound 391 compound 392 compound 393

；

Compound 394 compound 395 compound 396 compound 397 compound 398

；

Compound 399 Compound 400 Compound 401 Compound 402 Compound 403

；

Compound 404 compound 405 compound 406 compound 407 compound 408

；

Compound 409 compound 410 compound 411 compound 412 compound 413

；

Compound 414 compound 415 compound 416 compound 417 compound 418

；

Compound 419 compound 420 compound 421 compound 422 compound 423

；

Compound 424 compound 425 compound 426 compound 427 compound 428

；

Compound 429 compound 430 compound 431 compound 432 compound 433

；

Compound 434 compound 435 compound 436 compound 437 compound 438

；

Compound 439 compound 440 compound 441 compound 442 compound 443

；

Compound 444 compound 445 compound 446 compound 447 compound 448

；

Compound 449 compound 450 compound 451 compound 452 compound 453

；

Compound 454 compound 456 compound 457 compound 458 compound 459

；

Compound 460 compound 461 compound 462 compound 463 compound 464

；

Compound 465 compound 466 compound 467 compound 468 compound 469

；/>

Compound 470 compound 471 compound 472 compound 473 compound 474

；

Compound 475 compound 476 compound 477 compound 478 compound 479

；

Compound 480 compound 481 compound 482 compound 483 compound 484

；

Compound 485 compound 486 compound 487 compound 488 compound 489

；

Compound 490 compound 491 compound 492 compound 493 compound 494

；

Compound 495 compound 496 compound 497 compound 498 compound 499

；

Compound 500 compound 501 compound 502 compound 503 compound 504

；

Compound 505 compound 506 compound 507 compound 508 compound 509

；

Compound 510 compound 511 compound 512 compound 513 compound 514

；

Compound 515 compound 516 compound 517 compound 518 compound 519

；

Compound 520 compound 521 compound 522 compound 523 compound 524

；

Compound 525 compound 526 compound 527 compound 528 compound 529

；

Compound 530 compound 531 compound 532 compound 533 compound 534

；

Compound 535 compound 536 compound 537 compound 538 compound 539

；

Compound 540 compound 541 compound 542 compound 543 compound 544

；

Compound 545 compound 546 compound 547 compound 548 compound 549

；

Compound 550 compound 551 compound 552 compound 553 compound 554

；

Compound 555 compound 556 compound 557 compound 558 compound 559

；

Compound 560 compound 561 compound 562 compound 563 compound 564

；

Compound 565 compound 566 compound 567 compound 568 compound 569

；

Compound 570 compound 571 compound 572 compound 573 compound 574

；

Compound 575 compound 576 compound 577 compound 578 compound 579

；

Compound 580 compound 581 compound 582 compound 583 compound 584

；

Compound 585 compound 586 compound 587 compound 588 compound 589

；

Compound 590 compound 591 compound 592 compound 593 compound 594

；

Compound 595 compound 596 compound 597 compound 598 compound 599

；

Compound 600 compound 601 compound 602 compound 603 compound 604

；

Compound 605 compound 606 compound 607 compound 608 compound 609

；

Compound 610 compound 611 compound 612 compound 613 compound 614

；

Compound 615 compound 616 compound 617 compound 618 compound 619

；

Compound 620 compound 621 compound 622 compound 623 compound 624

；/>

Compound 625 compound 626 compound 627 compound 628 compound 629

；

Compound 630 compound 631 compound 632 compound 633 compound 634

；

Compound 635 compound 636 compound 637 compound 638 compound 639

；

Compound 640 compound 641 compound 642 compound 643 compound 644

；

Compound 645 compound 646 compound 647 compound 648 compound 649

；

Compound 650 compound 651 compound 652 compound 653 compound 654

；

Compound 655 compound 656 compound 657 compound 658 compound 659

；

Compound 660 compound 661 compound 662 compound 663 compound 664

；

Compound 665 compound 666 compound 667 compound 668 compound 669

；

Compound 670 compound 671 compound 672 compound 673 compound 674

；

Compound 675 compound 676 compound 677 compound 678 compound 679

；

Compound 680 compound 681 compound 682 compound 683 compound 684

；

Compound 685 compound 686 compound 687 compound 688 compound 689

；

Compound 690 compound 691 compound 692 compound 693 compound 694

；

Compound 695 compound 696 compound 697 compound 698 compound 699

；

Compound 700 compound 701 compound 702 compound 703 compound 704

；

Compound 705 compound 706 compound 707 compound 708 compound 709

；

Compound 710 compound 711 compound 712 compound 713 compound 714

；

Compound 715 compound 716 compound 717 compound 718 compound 719

；

Compound 720 compound 721 compound 722 compound 723 compound 724

；

Compound 725 compound 726 compound 727 compound 728 compound 729

；

Compound 730 compound 731 compound 732 compound 733 compound 734

；

Compound 735 compound 736 compound 737 compound 738 compound 739

；

Compound 740 compound 741 compound 742 compound 743 compound 744

；

Compound 745 compound 746 compound 747 compound 748 compound 749

；

Compound 750 compound 751 compound 752 compound 753 compound 754

；

Compound 755 compound 756 compound 757 compound 758 compound 759

；

Compound 760 compound 761 compound 762 compound 763 compound 764

；

Compound 765 compound 766 compound 767 compound 768 compound 769

；

Compound 780 compound 781 compound 782 compound 783 compound 784

；

Compound 785 compound 786 compound 787 compound 788 compound 789

；

Compound 790 compound 791 compound 792 compound 793 compound 794

；

Compound 795 compound 796 compound 797 compound 798 compound 799

；

Compound 800 compound 801 compound 802 compound 803 compound 804

；

Compound 805 compound 806 compound 807 compound 808 compound 809

；

Compound 810 compound 811 compound 812 compound 813 compound 814

；

Compound 815 compound 816 compound 817 compound 818 compound 819

；

Compound 820 compound 821 compound 822 compound 823 compound 824

；/>

Compound 825 compound 826 compound 827 compound 828 compound 829

；

Compound 830 compound 831 compound 832 compound 833 compound 834

；

Compound 835 compound 836 compound 837 compound 838 compound 839

；

Compound 840 compound 841 compound 842 compound 843 compound 844

；

Compound 845 compound 846 compound 847 compound 848 compound 849

；

Compound 850 compound 851 compound 852 compound 853 compound 854

；

Compound 855 compound 856 compound 857 compound 858 compound 859

；

Compound 860 compound 861 compound 862 compound 863 compound 864

；

Compound 865 compound 866 compound 867 compound 868 compound 869

；

Compound 870 compound 871 compound 872 compound 873 compound 874

；

Compound 875 compound 876 compound 877 compound 878 compound 879

；

Compound 880 compound 881 compound 882 compound 883 compound 884

；

Compound 885 compound 886 compound 887 compound 888 compound 889

；

Compound 890 compound 891 compound 892 compound 893 compound 894

；

Compound 895 compound 896 compound 897 compound 898 compound 899

；

Compound 900 compound 901 compound 902 compound 903 compound 904

；

Compound 905 compound 906 compound 907 compound 908 compound 909

；

Compound 910 compound 911 compound 912 compound 913 compound 914

；

Compound 915 Compound 916 Compound 917 Compound 918 Compound 919

；

Compound 920 compound 921 compound 922 compound 923 compound 924

；

Compound 925 compound 926 compound 927 compound 928 compound 929

；

Compound 930 compound 931 compound 932 compound 933 compound 934

；

Compound 935 compound 936 compound 937 compound 938 compound 939

；

Compound 940 compound 941 compound 942 compound 943 compound 944

；

Compound 945 compound 946 compound 947 compound 948 compound 949

；

Compound 950 compound 951 compound 952 compound 953 compound 954

；

Compound 955 compound 956 compound 957 compound 958 compound 959

；

Compound 960 compound 961 compound 962 compound 963 compound 964

；

Compound 965 compound 966 compound 967 compound 968 compound 969

；

Compound 970 compound 971 compound 972 compound 973 compound 974

；/>

Compound 975 compound 976 compound 977 compound 978 compound 979

；

Compound 980 compound 981 compound 982 compound 983 compound 984

；

Compound 985 compound 986 compound 987 compound 988 compound 989

；

Compound 990 compound 991 compound 992 compound 993 compound 994

；

Compound 995 compound 996 compound 997 compound 998 compound 999

；

Compound 1000 compound 1001 compound 1002 compound 1003 compound 1004 compound

；

Compound 1005 compound 1006 compound 1007 compound 1008 compound 1009

；

Compound 1010 compound 1011 compound 1012 compound 1013 compound 1014

；

Compound 1015 compound 1016 compound 1017 compound 1018 compound 1019

；

Compound 1020 compound 1021 compound 1022 compound 1023 compound 1024

；

Compound 1025 compound 1026 compound 1027 compound 1028 compound 1029

；

Compound 1030 compound 1031 compound 1032 compound 1033 compound 1034

；

Compound 1035 compound 1036 compound 1037 compound 1038 compound 1039

；

Compound 1040 compound 1041 compound 1042 compound 1043 compound 1044

；

Compound 1045 compound 1046 compound 1047 compound 1048 compound 1049

；

Compound 1050 compound 1051 compound 1052 compound 1053 compound 1054

；

Compound 1055 compound 1056 compound 1057 compound 1058 compound 1059

；

Compound 1060 compound 1061 compound 1062 compound 1063 compound 1064

；

Compound 1065 compound 1066 compound 1067 compound 1068 compound 1069

；

Compound 1070 compound 1071 compound 1072 compound 1073 compound 1074

；

Compound 1075 compound 1076 compound 1077 compound 1078 compound 1079

；

Compound 1080 compound 1081 compound 1082 compound 1083 compound 1084

；

Compound 1085 compound 1086 compound 1087 compound 1088 compound 1089

；

Compound 1090 compound 1091 compound 1092 compound 1093 compound 1094

；

Compound 1095 compound 1096 compound 1097 compound 1098 compound 1099

；

Compound 1110 compound 1111 compound 1112 compound 1113 compound 1114

；

Compound 1115 compound 1116 compound 1117 compound 1118 compound 1119

；

Compound 1120 compound 1121 compound 1122 compound 1123 compound 1124

；

Compound 1125 compound 1126 compound 1127 compound 1128 compound 1129

；

Compound 1130 compound 1131 compound 1132 compound 1133 compound 1134

；

Compound 1135 compound 1136 compound 1137 compound 1138 compound 1139

；

Compound 1140 compound 1141 compound 1142 compound 1143 compound 1144

；

Compound 1145 compound 1146 compound 1147 compound 1148 compound 1149

；

Compound 1150 compound 1151 compound 1152 compound 1153 compound 1154

；

Compound 1155 compound 1156 compound 1157 compound 1158 compound 1159

；

Compound 1160 compound 1161 compound 1162 compound 1163 compound 1164

；

Compound 1165 compound 1166 compound 1167 compound 1168 compound 1169

；

Compound 1170 compound 1171 compound 1172 compound 1173 compound 1174.

The preparation method and conditions of the boron-nitrogen-containing polycyclic aromatic hydrocarbon based on the five-membered heterocyclic ring structure of the present invention can refer to the steps and conditions of similar reactions in the field, and the present invention is preferably the following preparation method.

One embodiment of the method for preparing boron-nitrogen-containing polycyclic aromatic hydrocarbon based on five-membered heterocyclic ring structure of the above-listed specific structure of the present invention comprises the steps of:

bromine-substituted furan or thiophene and nitrogen-containing heterocyclic compound are taken as raw materials, and cesium carbonate (Cs) is added into the raw materials ₂ CO ₃ ) Tris (dibenzylideneacetone) dipalladium (Pd) ₂ (dba) ₃ ) Tri-tert-butylphosphine (t-Bu) ₃ P) and solvent o-xylene (o-xylene), and the preparation thereof Obtaining an intermediate;

adding tert-butyllithium (tBuLi) to a solution of the intermediate in tert-butylbenzene (t-Buph) followed by boron tribromide (BBr) ₃ ) Then adding N, N-Diisopropylethylamine (DIEA), and reacting to prepare the boron-containing nitrogen polycyclic aromatic hydrocarbon based on the five-membered heterocyclic structure;

the structural formula of the bromine-substituted furan or thiophene is one of the following structures:

；

the structural formula of the nitrogen-containing heterocyclic compound is one of the following structures:

、/>、/>、/>、/>、/>、/>、/>、/>、/>、/>、/>、/>、/>、/>、、/>、/>、/>、/>、/>、/>、/>、/>、、/>、/>、/>、/>、/> 、/>、/>、/>。

the synthetic general formula of the preparation method is as follows:

；

the preparation method is described in more detail below:

adding bromine-substituted furan or thiophene, nitrogen-containing heterocyclic compound and cesium carbonate (Cs) into a double-mouth bottle ₂ CO ₃ ) Tris (dibenzylideneacetone) dipalladium (Pd) ₂ (dba) ₃ ) Tri-tert-butylphosphine (t-Bu) ₃ P) and o-xylene (o-xylene) as solvent, heating at 130 ℃ in an oil bath under the protection of nitrogen for 12 h to stop the reaction, pouring the reaction mixture into distilled water, extracting with dichloromethane, concentrating, and separating by column chromatography to obtain an intermediate, wherein the intermediate is obtained through one-time, two-time and three-time carbon-nitrogen coupling; wherein the cesium carbonate (Cs ₂ CO ₃ ) The molar ratio to the substrate was 2:1, the tris (dibenzylideneacetone) dipalladium (Pd ₂ (dba) ₃ ) Molar ratio to substrate 1:20, said tri-tert-butylphosphine (t-Bu ₃ P) and a substrate are in a molar ratio of 1:20, wherein the substrate is bromine substituted furan or thiophene;

nitrogen protection and iceSlowly dropwise adding a tert-butyllithium (tBuLi) solution into an intermediate tert-butylbenzene (t-Buph) solution under water bath, heating to 60 ℃ and stirring for 2 hours, and pumping n-pentane in vacuum; then adding boron tribromide (BBr) at-30 deg.C ₃ ) Then, stirring the reaction system for 1 hour at room temperature, and finally adding N, N-Diisopropylethylamine (DIEA) at 0 ℃, stirring the reaction system for 6 hours at 130 ℃, and cooling to room temperature; methanol was added to the reaction system to quench residual boron tribromide (BBr ₃ ) The method comprises the steps of carrying out a first treatment on the surface of the Extracting the mixture with water and dichloromethane, combining the organic layers, concentrating in vacuo, purifying by column chromatography using a mixed eluent of dichloromethane/petroleum ether, and sublimating with a vacuum gradient to obtain the target compound; wherein the molar ratio of the tert-butyllithium (tBuLi) to the intermediate is 2:1, and the boron tribromide (BBr ₃ ) The molar ratio of the N, N-Diisopropylethylamine (DIEA) to the intermediate is 2:1, and the volume ratio of the dichloromethane to the petroleum ether is 1:20.

The invention relates to a preparation method of boron-nitrogen-containing polycyclic aromatic hydrocarbon based on a five-membered heterocyclic structure, wherein in the structural formula of the boron-nitrogen-containing polycyclic aromatic hydrocarbon based on the five-membered heterocyclic structure, Y is O or S, R ₅ Is that、/>、/>、/>Or->；

One specific embodiment of the preparation method of the boron-nitrogen-containing polycyclic aromatic hydrocarbon based on the five-membered heterocyclic ring structure comprises the following steps:

adding phenylboronic acid or p-tert-butylphenylboronic acid, carbonic acid to bromine-substituted furan or thiophenePotassium (K) ₂ CO ₃ ) Palladium tetraphenyl phosphine (Pd (PPh) ₃ ) ₄ ) Tetrahydrofuran (THF) and water (H) ₂ O), reacting to obtain an intermediate A;

adding a nitrogen-containing heterocyclic compound and cesium carbonate (Cs) to the intermediate A ₂ CO ₃ ) Tris (dibenzylideneacetone) dipalladium (Pd) ₂ (dba) ₃ ) Tri-tert-butylphosphine (t-Bu) ₃ P) and solvent o-xylene (o-xylene), and reacting to obtain an intermediate B;

adding tert-butyllithium (tBuLi) to the solution of intermediate B in tert-butylbenzene (t-Buph), followed by adding boron tribromide (BBr) ₃ ) Then adding N, N-Diisopropylethylamine (DIEA), and reacting to prepare the boron-containing nitrogen polycyclic aromatic hydrocarbon based on the five-membered heterocyclic structure;

；

、/>、/>、/>、/>、/>、/>、、/>、/>、/>、/>、/>、/>、/>、、/>、/>、/>、/>、/>、/>、/>、/>、/>、/>、/>、/>、/>、/> 、/>、/>、/>。

the synthetic general formula of the preparation method is as follows:

；

the preparation method is described in more detail below:

bromine-substituted furan or thiophene, phenylboronic acid or p-tert-butylphenylboronic acid, potassium carbonate (K) ₂ CO ₃ ) Tetraphenylphosphine palladium (Pd (PPh) ₃ ) ₄ ) Tetrahydrofuran (THF) and water (H) ₂ O) adding into a three-necked flask, heating and refluxing at 100deg.C in an oil bath under nitrogen protection for 12 h to stop the reaction, pouring the reaction mixture into distilled water, extracting with dichloromethane, concentrating, and performing column chromatographySeparating to obtain an intermediate A; wherein the molar ratio of phenylboronic acid or p-tert-butylphenylboronic acid to substrate is 1.1:1, and the potassium carbonate (K ₂ CO ₃ ) The molar ratio to substrate was 4:1, the tetraphenylphosphine palladium (Pd (PPh ₃ ) ₄ ) The molar ratio of the substrate to the substrate is 1:20, and the substrate is bromine substituted furan or thiophene;

in a double-necked flask, intermediate A and a nitrogen-containing heterocyclic compound, cesium carbonate (Cs ₂ CO ₃ ) Tris (dibenzylideneacetone) dipalladium (Pd) ₂ (dba) ₃ ) Tri-tert-butylphosphine (t-Bu) ₃ P) and solvent o-xylene (o-xylene), heating at 130 ℃ in an oil bath under the protection of nitrogen for 12 h to stop the reaction, pouring the reaction mixture into distilled water, extracting with dichloromethane, concentrating, and separating by column chromatography to obtain an intermediate B, wherein the intermediate B is obtained through one or two carbon-nitrogen couplings; wherein the cesium carbonate (Cs ₂ CO ₃ ) The molar ratio to intermediate A was 2:1, the tris (dibenzylideneacetone) dipalladium (Pd ₂ (dba) ₃ ) The molar ratio of the tri-tert-butylphosphine (t-Bu) to the intermediate A is 1:20 ₃ The molar ratio of P) to intermediate A is 1:20;

slowly dripping a tert-butyllithium (tBuLi) solution into a tert-butylbenzene (t-Buph) solution of an intermediate B under the protection of nitrogen and ice water bath, heating to 60 ℃ and stirring for 2 hours, and pumping n-pentane in vacuum; then adding boron tribromide (BBr) at-30 deg.C ₃ ) After that, the reaction system was stirred at room temperature for 1 hour; finally adding N, N-Diisopropylethylamine (DIEA) at the temperature of 0 ℃, stirring the reaction system at the temperature of 130 ℃ for 6 hours, and cooling to room temperature; methanol was added to the reaction system to quench residual boron tribromide (BBr ₃ ) The method comprises the steps of carrying out a first treatment on the surface of the Extracting the mixture with water and dichloromethane, combining the organic layers, concentrating in vacuo, purifying by column chromatography using a mixed eluent of dichloromethane/petroleum ether, and sublimating with a vacuum gradient to obtain the target compound; wherein the molar ratio of the tert-butyllithium (tBuLi) to the intermediate B is 2:1, the boron tribromide (BBr ₃ ) The molar ratio of the N, N-Diisopropylethylamine (DIEA) to the intermediate B is 2:1, the molar ratio of the N, N-diisopropylethylamine to the intermediate B is the molar ratio of the N-diisopropylethylamine to the intermediate B The volume ratio of dichloromethane to petroleum ether is 1:20.

The definition of X in the above-mentioned nitrogen-containing heterocyclic compound in the preparation method is identical to that in chemical formula 1, and will not be repeated here.

The invention relates to an application of boron-nitrogen-containing polycyclic aromatic hydrocarbon based on five-membered heterocyclic ring structure in preparing organic electroluminescent devices.

Further, the boron-nitrogen-containing polycyclic aromatic hydrocarbon based on the five-membered heterocyclic ring structure of the present invention is used as a light-emitting layer material of an organic electroluminescent device.

The beneficial effects of the invention are as follows:

the boron-nitrogen-containing polycyclic aromatic hydrocarbon based on the five-membered heterocyclic structure is a brand new MR-TADF material with a non-benzene aromatic ring with a five-membered heterocyclic structure as a molecular skeleton central ring, greatly enriches an MR-TADF material system, enhances the SOC due to the introduction of asymmetric rings (such as furan and thiophene rings) at the molecular skeleton center of the material, reduces delta EST, obviously reduces the efficiency roll-off, and further realizes higher photoelectric conversion efficiency of an OLED device.

Drawings

FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of compound 9 prepared in example 47 of the present invention.

Detailed Description

The present invention will be described in further detail with reference to specific examples, but embodiments of the present invention are not limited thereto. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to fall within the scope of the present invention.

Preparation example

Specific details of the preparation examples are described with reference to compounds 1, 17, 21, 29, 32, 41, 54, 59, 69, 76, 89, 103, 111, 126, 128, 145, 170, 176, 185, 189, 202, 215, 227, 241, 248, 263, 271, 284, 340, 376, 412, 438, 462, 534, 585, 611, 667, 713, 816, 878, 886, 925, 971, 1007, 1043, 1172, 9.

Example 1:

；

intermediate 1-A

Adding into 500 mL double-mouth bottle(3.04 g, 10 mmol), carbazole (3.67 g, 22 mmol), cesium carbonate (13.04 g, 40 mmol), tris (dibenzylideneacetone) dipalladium (9.2 g, 1 mmol), tri-tert-butylphosphine (2.00 g, 1 mmol) and ortho-xylene 300 mL. Heating at 130 ℃ in an oil bath for 12 hours under the protection of nitrogen to stop the reaction, pouring the reaction mixture into distilled water, extracting with dichloromethane, concentrating, and separating by using a developing solvent column chromatography of dichloromethane and petroleum ether (the volume ratio of the dichloromethane to the petroleum ether is 2:1) to obtain an intermediate 1-A3.97 g (the yield is 84%);

a solution of tert-butyllithium (7.8 mL, 10 mmol) was slowly added dropwise to a solution of intermediate 1-A (2.37 g, 5 mmol) in tert-butylbenzene (40 mL) under nitrogen and ice-water bath, followed by heating to 60℃and stirring for 2 hours, and n-pentane was removed in vacuo. Then, boron tribromide (1 mL, 10 mmol) was added at-30 ℃ and the reaction system was stirred at room temperature for 1 hour. Finally, adding N, N-diisopropylethylamine (1.4 mL, 10 mmol) at the temperature of 0 ℃, stirring the reaction system at the temperature of 130 ℃ for 6 hours, and cooling to the room temperature. 2 mL methanol was added to the reaction system to quench residual boron tribromide. The mixture was extracted with 40 mL water and 40 mL dichloromethane, the organic layers were combined, concentrated in vacuo, and purified by column chromatography using a mixed eluent of dichloromethane/petroleum ether (dichloromethane and petroleum ether at a volume ratio of 1:20), followed by sublimation using a vacuum gradient to give compound 1 (1.06 g) in 26% yield.

Example 2:

；

intermediate 1-A ^， Intermediate 1-B

Adding into 500 mL double-mouth bottle（6.40 g, 20 mmol），/>(5.65 g, 22 mmol), cesium carbonate (13.04 g, 40 mmol), tris (dibenzylideneacetone) dipalladium (9.2 g, 1 mmol), tri-tert-butylphosphine (2.00 g, 1 mmol) and ortho-xylene 300 mL. Heating at 130deg.C in oil bath under nitrogen protection for 12 hr to stop reaction, pouring the reaction mixture into distilled water, extracting with dichloromethane, concentrating, and separating by column chromatography with developing solvent of dichloromethane and petroleum ether (volume ratio of dichloromethane to petroleum ether is 2:1) to obtain intermediate 1-A ^， 8.08 g (yield 83%).

Into a 250 mL double-necked flask was added intermediate 1-A ^， (4.97 g, 10 mmol), carbazole (1.84 g, 11 mmol), cesium carbonate (6.52 g,20 mmol), tris (dibenzylideneacetone) dipalladium (2.3 g, 0.25 mmol), tri-tert-butylphosphine (0.5 g, 0.25 mmol) and ortho-xylene 150 ml. Under the protection of nitrogen, heating at 130 ℃ for 12 hours in an oil bath to stop the reaction, pouring the reaction mixture into distilled water, extracting with dichloromethane, concentrating, and separating by using a developing agent column chromatography of dichloromethane and petroleum ether (the volume ratio of the dichloromethane to the petroleum ether is 2:1) to obtain an intermediate 1-B4.80 g (the yield is 82%).

A solution of tert-butyllithium (7.8 mL, 10 mmol) was slowly added dropwise to a solution of intermediate 1-B (2.93 g, 5 mmol) in tert-butylbenzene (40 mL) under nitrogen and ice water, followed by heating to 60℃and stirring for 2 hours, and n-pentane was removed in vacuo. Then, boron tribromide (1 mL, 10 mmol) was added at-30 ℃ and the reaction system was stirred at room temperature for 1 hour. Finally, adding N, N-diisopropylethylamine (1.4 mL, 10 mmol) at the temperature of 0 ℃, stirring the reaction system at the temperature of 130 ℃ for 6 hours, and cooling to the room temperature. 2 mL methanol was added to the reaction system to quench residual boron tribromide. The mixture was extracted with 40 mL water and 40 mL dichloromethane, the organic layers were combined, concentrated in vacuo, and purified by column chromatography on a mixed eluent of dichloromethane/petroleum ether (dichloromethane/petroleum ether volume ratio 1:20) followed by sublimation using a vacuum gradient to give compound 17 (0.72 g) in 28% yield.

Example 3:

in analogy to the preparation of compound 17Is prepared from raw materials including->And the carbazolyl carbon nitrogen is coupled to obtain an intermediate, and the compound 21 is finally prepared with the yield of 29%.

Example 4:

in analogy to the preparation of compound 17Is prepared from raw materials including- >After coupling with carbazole carbon nitrogen to give intermediate, compound 29 was finally prepared in 26% yield.

Example 5:

in analogy to the preparation of compound 17Is prepared from raw materials including->After coupling with carbazole carbon nitrogen to give intermediate, compound 32 was finally prepared in 28% yield. />

Example 6:

in analogy to the preparation of compound 17Is prepared from raw materials including->After the intermediate is obtained by coupling with carbazole carbon nitrogen, the mostCompound 41 was obtained in 24% yield.

Example 7:

in analogy to the preparation of compound 17Is prepared from raw materials including->After coupling with carbazole carbon nitrogen to give intermediate, compound 54 was finally prepared in 24% yield.

Example 8:

in analogy to the preparation of compound 17Is prepared from raw materials including->After coupling with carbazole carbon nitrogen to give intermediate, compound 59 was finally prepared in 28% yield.

Example 9:

in analogy to the preparation of compound 17Is prepared from raw materials including->And->After coupling carbon and nitrogen to give intermediate, compound 69 was finally prepared in 27% yield.

Example 10:

in analogy to the preparation of compound 17Is prepared from raw materials including->And->After coupling carbon and nitrogen to afford intermediate, compound 76 was finally prepared in 25% yield.

Example 11:

in analogy to the preparation of compound 17Is prepared from raw materials including->Andafter coupling carbon and nitrogen to give intermediate, compound 89 was finally prepared in 28% yield.

Example 12:

in analogy to the preparation of compound 17Is prepared from raw materials including->And->After coupling carbon and nitrogen to give intermediate, compound 103 was finally prepared in 26% yield.

Example 13:

in analogy to the preparation of compound 17Is prepared from raw materials including->And->After coupling carbon and nitrogen to give an intermediate, compound 111 was finally prepared in 23% yield.

Example 14:

in analogy to the preparation of compound 17Is prepared from raw materials including->And->After coupling carbon and nitrogen to afford intermediate, compound 126 was finally prepared in 28% yield.

Example 15:

in analogy to the preparation of compound 17Is prepared from raw materials including->And->After coupling carbon and nitrogen to give intermediate, compound 128 was finally prepared in 27% yield.

Example 16:

in analogy to the preparation of compound 17Is prepared from raw materials including->And->After coupling carbon and nitrogen to afford intermediate, compound 145 was finally prepared in 25% yield.

Example 17:

in analogy to the preparation of compound 17 Is prepared from raw materials including->And->After coupling carbon and nitrogen to afford intermediate, compound 170 was finally prepared in 28% yield.

Example 18:

in analogy to the preparation of compound 17Is prepared from raw materials including->And->After coupling carbon and nitrogen to afford intermediate, compound 176 was finally prepared in 27% yield.

Example 19:

in analogy to the preparation of compound 17Is prepared from raw materials including->And->After coupling carbon and nitrogen to afford intermediate, compound 185 was finally prepared in 24% yield.

Example 20:

in analogy to the preparation of compound 17Is prepared from raw materials including->Andafter coupling carbon and nitrogen to give intermediate, compound 189 was finally prepared in 24% yield.

Example 21:

and chemical treatmentCompound 17 preparation reactions were similar toIs prepared from raw materials including->And->After coupling carbon and nitrogen to give an intermediate, compound 202 was finally prepared in 28% yield.

Example 22:

in analogy to the preparation of compound 17Is prepared from raw materials including->And->After coupling carbon and nitrogen to afford intermediate, compound 215 was finally prepared in 27% yield. />

Example 23:

in analogy to the preparation of compound 17Is prepared from raw materials including->And->After coupling carbon and nitrogen to afford intermediate, compound 227 was finally prepared in 26% yield.

Example 24:

in analogy to the preparation of compound 17Is prepared from raw materials including->And->After coupling carbon and nitrogen to give an intermediate, compound 241 was finally prepared in 25% yield.

Example 25:

in analogy to the preparation of compound 17Is prepared from raw materials including->And->After coupling carbon and nitrogen to afford intermediate, compound 248 was finally prepared in 22% yield.

Example 26:

in analogy to the preparation of compound 17Is prepared from raw materials including->And->After coupling carbon and nitrogen to give intermediate, compound 263 was finally prepared in 24% yield.

Example 27:

in analogy to the preparation of compound 17Is prepared from (by weight parts)>And (2) and->After coupling carbon and nitrogen to give intermediate, compound 271 was finally prepared in 28% yield.

Example 28:

；

intermediate 2-A intermediate 2-B

Will be(7.67 g,20 mmol), phenylboronic acid (2.68 g,22 mmol), potassium carbonate (11.03 g,80 mmol), tetraphenylphosphine palladium (1.2 g,1 mmol), tetrahydrofuran (200 mL) and water (50 mL) were added to a 500 mL three-necked flask, the reaction was stopped by heating and refluxing at 100℃in an oil bath for 12 hours under nitrogen protection, the reaction mixture was poured into distilled water, extracted with methylene chloride, concentrated and then separated by column chromatography with a developing solvent of methylene chloride and petroleum ether (volume ratio of methylene chloride to petroleum ether: 2:1) to obtain intermediate 2-A5.09 g (yield: 67%). Intermediate 2-A is prepared from- >Carbon-carbon coupling with phenylboronic acid.

In a 500 mL double vial was added intermediate 2-A (3.67 g, 10 mmol),(4.29 g, 22 mmol), cesium carbonate (13.04 g, 40 mmol), tris (dibenzylideneacetone) dipalladium (9.2 g, 1 mmol), tri-tert-butylphosphine (2.00 g, 1 mmol) and ortho-xylene 150 mL. Under the protection of nitrogen, heating at 130 ℃ for 12 hours in an oil bath to stop the reaction, pouring the reaction mixture into distilled water, extracting with dichloromethane, concentrating, and separating by using a developing agent column chromatography of dichloromethane and petroleum ether (the volume ratio of the dichloromethane to the petroleum ether is 2:1) to obtain an intermediate 2-B5.24 g (yield 86%).

A solution of tert-butyllithium (7.8 mL, 10 mmol) was slowly added dropwise to a solution of intermediate 2-B (3.05 g, 5 mmol) in tert-butylbenzene (40 mL) under nitrogen and ice-water bath, then heated to 60℃and stirred for 2 hours, and n-pentane was removed in vacuo. Then, boron tribromide (1 mL, 10 mmol) was added at-30 ℃ and the reaction system was stirred at room temperature for 1 hour. Finally, adding N, N-diisopropylethylamine (1.4 mL, 10 mmol) at the temperature of 0 ℃, stirring the reaction system at the temperature of 130 ℃ for 6 hours, and cooling to the room temperature. 2mL of methanol was added to the reaction system to quench residual boron tribromide. The mixture was extracted with 40 mL water and 40 mL dichloromethane, the organic layers were combined, concentrated in vacuo, and purified by column chromatography on a mixed eluent of dichloromethane/petroleum ether (volume ratio of dichloromethane to petroleum ether 1:20) followed by sublimation using a vacuum gradient to give compound 284 (0.73 g) in 27% yield. The compound 284 obtained from intermediate 2-B can be obtained by reference to the description of scheme on page 17500 of "angel. Chem. Int. Ed. 2020, 59, 17499-17503".

Example 29:

similar to the preparation of compound 284 toAs a raw material, the coupling of carbon and carbon is finished by the p-tert-butyl phenylboronic acid, and then the coupling is successively carried out with +.>And carbazole to give an intermediate, and finally preparing the obtained compound 340 with a yield of 28%.

Example 30:

；

intermediate 2-B ^，， Intermediate 2-B ^，

；

Intermediate 2-B

Adding into 500 mL double-mouth bottle(19.18 g, 50 mmol), diphenylamine (9.31 g, 55 mmol), cesium carbonate (32.60 g, 100)mmol), tris (dibenzylideneacetone) dipalladium (11.5 g, 1.25 mmol), tri-tert-butylphosphine (2.50 g, 1.25 mmol) and ortho-xylene 380 mL. Heating at 130deg.C in oil bath under nitrogen protection for 12 hr to stop reaction, pouring the reaction mixture into distilled water, extracting with dichloromethane, concentrating, and separating by column chromatography with dichloromethane and petroleum ether (2:1) developing solvent to obtain intermediate 2-B ^，， 19.55 g (yield 83%).

Into a 250 mL double-mouth bottle, an intermediate 2-B is added ^，，（9.42 g, 20 mmol），(6.23 g, 22 mmol), cesium carbonate (13.04 g, 40 mmol), tris (dibenzylideneacetone) dipalladium (4.6 g, 0.5 mmol), tri-tert-butylphosphine (1.00 g, 0.5 mmol) and ortho-xylene 150 mL. Heating at 130deg.C in oil bath under nitrogen protection for 12 hr to stop reaction, pouring the reaction mixture into distilled water, extracting with dichloromethane, concentrating, and separating by column chromatography with developing solvent of dichloromethane and petroleum ether (volume ratio of dichloromethane to petroleum ether is 2:1) to obtain intermediate 2-B ^， 11.05 g (82% yield).

Into a 250 mL double-mouth bottle, an intermediate 2-B is added ^， (6.74 g, 10 mmol), carbazole (1.84 g, 11 mmol), cesium carbonate (6.52 g, 20 mmol), tris (dibenzylideneacetone) dipalladium (2.30 g, 0.25 mmol), tri-tert-butylphosphine (0.50 g, 0.25 mmol) and ortho-xylene 75 mL. Under the protection of nitrogen, heating at 130 ℃ in an oil bath for 12 h to stop the reaction, pouring the reaction mixture into distilled water, extracting with dichloromethane, concentrating, and separating by column chromatography with dichloromethane and petroleum ether (2:1) developing agent to obtain an intermediate 2-B6.38 g (yield 84%).

A solution of tert-butyllithium (7.8 mL, 10 mmol) was slowly added dropwise to a solution of intermediate 2-B (2.93 g, 5 mmol) in tert-butylbenzene (40 mL) under nitrogen and ice water bath, then heated to 60℃and stirred for 2 hours, and n-pentane was removed in vacuo. Then, boron tribromide (1 mL, 10 mmol) was added at-30 ℃ and the reaction system was stirred at room temperature for 1 hour. Finally, adding N, N-diisopropylethylamine (1.4 mL, 10 mmol) at the temperature of 0 ℃, stirring the reaction system at the temperature of 130 ℃ for 6 hours, and cooling to the room temperature. 2 mL methanol was added to the reaction system to quench residual boron tribromide. The mixture was extracted with 40 mL water and 40 mL dichloromethane, the organic layers were combined, concentrated in vacuo, and purified by column chromatography on a mixed eluent of dichloromethane/petroleum ether (volume ratio of dichloromethane to petroleum ether 1:20) followed by sublimation using a vacuum gradient to give compound 376 (1.93 g) in 28% yield.

Example 31:

similar to the preparation of Compound 376As raw materials, carbazole and +.>And carbazole to give intermediate, compound 412 was finally prepared in 26% yield.

Example 32:

similar to the preparation of Compound 376Is prepared from raw materials including->And->And carbazole reaction to give intermediate, compound 438 was finally prepared in 27% yield.

Example 33:

similar to the preparation of Compound 376As raw materials, sequentially mixing with phenylenediamine and +.>And carbazole carbon nitrogen coupling to give intermediate, compound 462 was finally prepared in 24% yield.

Example 34:

and chemical treatmentCompound 376 is prepared in a similar reaction toIs prepared from raw materials including->And->And carbazole carbon nitrogen coupling to obtain intermediate, and finally preparing compound 534 with yield of 25%.

Example 35:

similar to the preparation of compound 284 toAs raw material, firstly, after finishing carbon-carbon coupling with phenylboronic acid, then successively combining with +.>And->After coupling carbon and nitrogen to give intermediate, compound 585 was finally prepared in 23% yield.

Example 36:

similar to the preparation of compound 284 toAs a raw material, the coupling of carbon and carbon is finished by the p-tert-butyl phenylboronic acid, and then the coupling is successively carried out with +. >And->After coupling carbon and nitrogen to give intermediate, compound 611 was finally prepared in 27% yield.

Example 37:

similar to the preparation of Compound 376As raw materials, sequentially mixing with phenylenediamine and +.>A kind of electronic device with high-pressure air-conditioning systemAfter coupling carbon and nitrogen to give intermediate, compound 667 was finally prepared in 28% yield.

Example 38:

similar to the preparation of Compound 376As raw materials, carbazole and +.>A kind of electronic device with high-pressure air-conditioning systemAfter coupling carbon and nitrogen to give intermediate, compound 713 was finally prepared in 25% yield.

Example 39:

similar to the preparation of compound 284 toAs a raw material, the coupling of carbon and carbon is finished by the p-tert-butyl phenylboronic acid, and then the coupling is successively carried out with +.>And->After coupling carbon and nitrogen to afford intermediate, compound 816 was finally prepared in 22% yield.

Example 40:

similar to the preparation of Compound 376As raw materials, carbazole and +.>Is->After coupling carbon and nitrogen to give intermediate, compound 878 was finally prepared in 28% yield.

Example 41:

similar to the preparation of compound 284 toAs raw material, firstly, the para-tert-butyl phenylboronic acid is used for completing carbon-carbon coupling, then the para-tert-butyl phenylboronic acid is used for preparing the material>And->After coupling with carbon nitrogen to give intermediate, compound 886 was finally prepared in 25% yield.

Example 42:

similar to the preparation of compound 284 toAs raw material, firstly, after finishing carbon-carbon coupling with phenylboronic acid, then successively combining with +.>And->After coupling carbon and nitrogen to give an intermediate, compound 925 was finally prepared in 23% yield.

Example 43:

similar to the preparation of compound 284 toAs a raw material, the coupling of carbon and carbon is finished by the p-tert-butyl phenylboronic acid, and then the coupling is successively carried out with +.>And->Carbon-nitrogen couplingAfter the intermediate was obtained, compound 971 was finally obtained in 26% yield.

Example 44:

similar to the preparation of Compound 376As raw materials, sequentially combined with phenylenediamine andafter coupling carbon and nitrogen to give intermediate, compound 1007 was finally prepared in 23% yield.

Example 45:

similar to the preparation of Compound 376As raw materials, carbazole and +.>A kind of electronic device with high-pressure air-conditioning systemAfter coupling carbon and nitrogen to give intermediate, compound 1043 was finally prepared in 23% yield.

Example 46:

similar to the preparation of Compound 376As raw materials, with diphenylamine and +.>Is->After coupling carbon and nitrogen to give intermediate, compound 1172 was finally prepared in 26% yield.

Example 47:

；

intermediate products

Similar to the preparation of Compound 1 Is prepared from (a) and (b) herba Cistanchis>After coupling carbon and nitrogen to give an intermediate, compound 9 was finally prepared in 28% yield.

The nuclear magnetic resonance spectrum of compound 9 prepared in this example is shown in fig. 1,1H NMR (500 MHz, DMSO-d 6) δ8.93 (s, 1H), 8.82 (s, 1H), 8.77 (s, 1H), 8.61 (d, j=1.7 Hz, 1H), 8.53 (s, 1H), 8.41 (s, 1H), 8.22 (d, j=8.5 Hz, 1H), 8.01 (d, j=8.6 Hz, 1H), 7.81 (d, j=8.6 Hz, 1H), 7.70-7.68 (m, 1H), 7.58 (s, 1H), 1.62 (d, j=13.3 Hz, 18H), 1.49 (d, j=2.7 Hz, 18H).

TABLE 1 summary of synthetic example product data

Compounds of formula (I)	Molecular weight (m/Z)	Elemental analysis (%) (C, H, N, O)	Yield (%)
				Compound 1	406.21	C, 82.71; H, 3.79; N, 6.81; O, 3.87	26
Compound 17	512.01	C, 79.78; H, 3.42; N, 5.39; O, 3.20	28
				Compound 21	522.31	C, 85.17; H, 4.35; N, 5.45; O, 3.13	29
Compound 29	662.31	C, 85.07; H, 4.19; N, 4.30	26
				Compound 32	644.30	C, 87.67; H, 3.83; N, 4.43; O, 2.42	28
Compound 41	407.01	C, 79.72; H, 3.39; N, 10.41; O, 3.87	24
				Compound 54	424.23	C, 73.72; H, 3.01; N, 13.30	24
Compound 59	572.35	C, 86.10; H, 4.49; N, 4.74; O, 2.74	28
				Compound 69	480.29	C, 77.62; H, 4.49; N, 5.75; O, 3.41	27
Compound 76	874.33	C, 85.21; H, 6.86; N, 3.25	25
				Compound 89	784.38	C, 84.29; H, 4.70; N, 3.51; O, 2.07	28
Compound 103	570.25	C, 77.78; H, 4.12; N, 4.98	26
				Compound 111	586.24	C, 75.89; H, 3.90; N, 4.71; O, 2.75	23
Compound 126	702.12	C, 85.58; H, 4.52; N, 3.92	28
				Compound 128	730.20	C, 87.01; H, 5.31; N, 3.89; O, 2.16	27
Compound 145	439.22	C, 73.72; H, 3.28; N, 9.49; O, 3.60	25
				Compound 170	614.13	C, 85.87; H, 5.01; N, 4.48; O, 2.63	28
Compound 176	502.16	C, 67.21; H, 3.08; N, 5.50; O, 6.31	27
				Compound 185	670.32	C, 71.86; H, 5.80; N, 4.12	24
Compound 189	1094.45	C, 74.61; H, 5.88; N, 2.50; O, 1.41	24
				Compound 202	528.23	C, 77.41; H, 3.20; N, 5.39; O, 6.15	28
Compound 215	554.29	C, 80.04; H, 4.11; N, 5.14; O, 8.75	27
				Compound 227	660.31	C, 85.57; H, 3.78; N, 4.18; O, 4.80	26
Compound 241	822.15	C, 68.92; H, 3.38; N, 3.47	25
				Compound 248	551.18	C, 69.73; H, 3.35; N, 7.70; O, 2.95	22
Compound 263	456.20	C, 68.32; H, 2.85; N, 12.37; O, 7.09	24
				Compound 271	698.17	C, 70.49; H, 3.36; N, 4.09	28
Compound 284	538.34	C, 84.65; H, 5.01; N, 5.26; O, 2.92	27
				Compound 340	644.09	C, 81.87; H, 4.60; N, 4.39; O, 2.53	28
Compound 376	689.37	C, 85.23; H, 4.61; N, 6.02; O, 2.36	28
				Compound 412	827.37	C, 85.72; H, 4.06; N, 5.02	26
Compound 438	921.28	C, 87.40; H, 5.33; N, 4.50; O, 1.72	27
				Compound 462	574.31	C, 81.43; H, 4.10; N, 9.83; O, 2.75	24
Compound 534	865.48	C, 84.72; H, 5.67; N, 4.89	25
				Compound 585	556.29	C, 79.75; H, 4.59; N, 5.08; O, 2.82	23
Compound 611	820.61	C, 83.50; H, 7.91; N, 3.46	27
				Compound 667	951.24	C, 84.64; H, 4.80; N, 4.47; O, 1.62	28
Compound 713	735.31	C, 79.88; H, 4.03; N, 5.75	25
				Compound 816	862.52	C, 87.58; H, 5.90; N, 3.29; O, 1.87	22
Compound 878	604.26	C, 77.38; H, 3.54; N, 9.36; O, 2.60	28
				Compound 886	746.47	C, 86.73; H, 5.87; N, 3.79; O, 2.17	25
Compound 925	578.18	C, 70.63; H, 3.36; N, 4.88; O, 5.51	23
				Compound 971	802.41	C, 74.79; H, 6.48; N, 3.42	26
Compound 1007	1261.52	C, 76.14; H, 5.70; N, 3.38; O, 1.23	23
				Compound 1043	693.28	C, 79.54; H, 3.43; N, 6.01; O, 4.66	23
Compound 1172	865.02	C, 73.72; H, 3.70; N, 4.94	26
				Compound 9	646.25	C, 81.61; H, 7.36; N, 4.35	28

Device embodiment

The OLED structure includes a first electrode and a second electrode, and an organic material layer between the two electrodes. The organic material layer may be divided into a plurality of regions, and the organic material layer may include a hole transport region, a light emitting layer, and an electron transport region.

In particular embodiments, a substrate may be used below the first electrode or above the second electrode. The substrates are all glass or polymer materials with excellent mechanical strength, thermal stability, water resistance and transparency. A Thin Film Transistor (TFT) may be provided on a substrate for a display.

The first electrode may be formed by sputtering or depositing a material serving as the first electrode on the substrate. When the first electrode is used as the anode, indium Tin Oxide (ITO), indium Zinc Oxide (IZO), tin dioxide (SnO) ₂ ) An oxide transparent conductive material such as zinc oxide (ZnO), and any combination thereof. When the first electrode is used as the cathode, metals or alloys such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), and magnesium-silver (Mg-Ag) and any combination thereof can be used.

The organic material layer may be formed on the electrode by vacuum thermal evaporation, spin coating, printing, or the like. The compounds used as the organic material layer may be small organic molecules, large organic molecules and polymers, and combinations thereof.

The hole transport region is located between the anode and the light emitting layer. The hole transport region may be a Hole Transport Layer (HTL) of a single layer structure including a single layer hole transport layer containing only one compound and a single layer hole transport layer containing a plurality of compounds. The hole transport region may have a multilayer structure including at least one of a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), and an Electron Blocking Layer (EBL); wherein the HIL is located between the anode and the HTL and the EBL is located between the HTL and the light emitting layer.

The material of the hole transport region may be selected from, but is not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or conductive dopant containing polymers such as polystyrene, polyaniline/dodecylbenzenesulfonic acid (Pani/DBSA), poly (3, 4-ethylenedioxythiophene)/poly (4-styrenesulfonate) (PED 0T/PSS), polyaniline/camphorsulfonic acid (Pani/CSA), polyaniline/poly (4-styrenesulfonate) (Pani/PSS), or aromatic amine derivatives; or any combination of the foregoing.

Wherein the aromatic amine derivative is any one or more of the compounds represented by HT-1 through HT-19 below;

；

HT-1 HT-2 HT-3 HT-4

；

HT-5 HT-6 HT-7 HT-8

；

HT-9 HT-10 HT-11 HT-12

；/>

HT-13 HT-14 HT-15 HT-16

；

HT-17 HT-18 HT-19

the hole injection layer is located between the anode and the hole transport layer. The hole injection layer may be a single compound material or a combination of a plurality of compounds. For example, the hole injection layer may employ one or more of the compounds HT-1 through HT-19 described above, or one or more of the compounds HI-1 through HI-3 described below; one or more compounds of HT-1 through HT-19 may also be used to dope one or more of HI-1 through HI-3 described below.

；

HI-1 HI-2 HI-3

The light-emitting layer includes a light-emitting guest material (Dopant) capable of emitting light of different wavelength spectrums, and a Host material (Host) at the same time. The light emitting layer may be a single color light emitting layer emitting a single color of red, green, blue, or the like. The plurality of monochromatic light emitting layers with different colors can be arranged in a plane according to the pixel pattern, or can be stacked together to form a color light emitting layer. When the light emitting layers of different colors are stacked together, they may be spaced apart from each other or may be connected to each other. The light emitting layer may be a single color light emitting layer capable of simultaneously emitting different colors such as red, green, and blue.

According to different technologies, the luminescent layer material can be made of different materials such as fluorescent electroluminescent material, phosphorescent electroluminescent material, thermal activation delayed fluorescence luminescent material and the like. In an OLED device, a single light emitting technology may be used, or a combination of different light emitting technologies may be used. The different luminescent materials classified by the technology can emit light of the same color, and can also emit light of different colors.

In the present invention, the protected compounds are all MR-TADF materials, so the luminescent layer adopts a heat-activated delayed luminescence technology, and the main material of the luminescent layer is selected from, but not limited to, one or more of the following TH-1 to TH-31.

；

TH-1 TH-2 TH-3 TH-4

；

TH-5 TH-6 TH-7 TH-8

；

TH-9 TH-10 TH-11 TH-12

；

TH-13 TH-14 TH-15 TH-16

；

TH-17 TH-18 TH-19 TH-20

；

TH-21 TH-22 TH-23 TH-24

；

TH-25 TH-26 TH-27 TH-28

；

TH-29 TH-30 TH-31

An Electron Blocking Layer (EBL) is located between the hole transport layer and the light emitting layer. The electron blocking layer may employ, but is not limited to, a mixture of one or more of the compounds HT-1 through HT-19 described above.

The OLED organic material layer may further include an electron transport region between the light emitting layer and the cathode. The electron transport region may be an Electron Transport Layer (ETL) of a single layer structure including a single layer electron transport layer containing only one compound and a single layer electron transport layer containing a plurality of compounds. The electron transport region may also be a multilayer structure including at least one of an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), and a Hole Blocking Layer (HBL).

The electron transport layer material may be selected from, but is not limited to, one or more combinations of ET-1 through ET-19 listed below.

；

ET-1 ET-2 ET-3 ET-4

；

ET-5 ET-6 ET-7 ET-8

；

ET-9 ET-10 ET-11 ET-12

；

ET-13 ET-14 ET-15 ET-16

；

ET-17 ET-18 ET-19

A Hole Blocking Layer (HBL) is located between the electron transport layer and the light emitting layer. The hole blocking layer may employ, but is not limited to, a mixture of one or more of the compounds ET-1 to ET-19 described above.

An electron injection layer may also be included in the device between the electron transport layer and the cathode, the electron injection layer material including, but not limited to, a combination of one or more of the following.

LiQ (lithium 8-hydroxyquinoline), liF, naCl, csF, li ₂ O，Cs ₂ CO ₃ ，BaO，Na，Li，Ca，Mg。

The preparation process of the organic electroluminescent device comprises the following steps: ultrasonic treating the glass plate coated with the ITO transparent conductive layer in a commercial cleaning agent, flushing in deionized water, ultrasonic degreasing in a mixed solvent of acetone and ethanol, baking in a clean environment until water is completely removed, cleaning with ultraviolet light and ozone, and bombarding the surface with a low-energy cation beam; placing the glass substrate with anode in vacuumVacuum pumping to less than 10 ^-5 Pa, vacuum evaporating HT/HI (97/3,w/w) mixture as hole injection layer on the anode layer film, wherein the evaporation rate is 0.1 nm/s, and the evaporation film thickness is 10 nm; vacuum evaporation HT is carried out on the hole injection layer to serve as a hole transmission layer of the device, the evaporation rate is 0.1 nm/s, and the thickness of the evaporation film is 60 nm; vacuum evaporation HT is carried out on the hole transport layer to serve as an electron blocking layer of the device, the evaporation rate is 0.1 nm/s, and the thickness of the evaporation film is 5 nm; vacuum vapor plating a light emitting layer of the device on the electron blocking layer, wherein the light emitting layer comprises a host material and an MR-TADF guest material, and vapor plating a compound TH of 30 nm by utilizing a multi-source co-evaporation method: an MR-TADF guest material (100: 3,w/w) binary mixture is used as a light-emitting layer; vacuum evaporating ET of 5 nm as hole blocking layer and compound ET of 25 nm as electron transport layer with evaporation rate of 0.l nm/s and thickness of 30 nm; liF with the thickness of 0.5 nm is vacuum evaporated on an Electron Transport Layer (ETL) to serve as an electron injection layer, 150 nm of metal aluminum is used as a cathode, the total evaporation rate of LiF is controlled to be 0.1 nm/s, and the evaporation rate of a metal electrode is controlled to be 1 nm/s.

The structure of the organic electroluminescent device in the embodiment of the device is as follows: ITO/HI (HT-4: HI-3 (97/3,w/w), 10 nm)/HT (HT-4, 30 nm)/EBL (HT-14, 10 nm)/Host (TH-5): 3 wt% (MR-TADF) (100:3, w/w,30 nm)/HBL (ET-13, 10 nm)/ET (ET-17: liQ (50/50, w/w), 30 nm)/LiF (0.5 nm)/Al (150 nm).

The MR-TADF guest materials in the devices DD1, DD2, DD3 and DD4 of the comparative example have the following structures:

；

MR-1 MR-2 MR-3 MR-4

the invention applies to the embodiment devices D1, D2, D3, D4, D5, D6, D7, D8, D9, D10, D11, D12, D13, D14, D15, D16, D17, D18, D19, D20, D21, D22, D23, D24, D25, D26, D27, D28, D29, D30, D31, D32, D33, D34, D35, D36, D37, D38, D39, D40, D41, D42, D43, D44, D45, D46, D47, the organic photoelectric functional material compounds 1, 17, 21, 29, 32, 41, 54, 59, 69, 76, 89, 103, 111, 126, 128, 145, 170, 176, 185, 189, 202, 215, 227, 241, 248, 263, 271, 284, 340, 376, 412, 438, 462, 534, 585, 611, 667, 713, 816, 878, 886, 925, 971, 1007, 1043, 1172, 9, each of which is prepared by substituting the guest materials MR-1, MR-2, MR-3, and MR-4 of the light emitting layer in comparative example 1 with a non-benzene aromatic ring such as furan or thiophene.

The organic electroluminescent device prepared by the above procedure was subjected to the following performance measurement: the turn-on voltage and half-width of the organic electroluminescent devices prepared in comparative examples DD1 to DD4 and application examples D1 to D47 were measured using a digital source meter and a luminance meter at the same luminance. Specifically, the luminance of the organic electroluminescent device was measured to reach l cd/m by boosting the voltage at a rate of 0.1. 0.1V per second ² The voltage at that time is the turn-on voltage; 10 cd/m ² Obtaining the maximum luminous peak wavelength and half-peak width; the External Quantum Efficiency (EQE) of the device is calculated from the current density, brightness and electro-spectral combined with the visual function in the case of the light emission as a langerhans distribution. The lifetime test of LT90 is as follows: using a luminance meter at 1000 cd/m ² Under the condition of brightness, constant current is kept, and the brightness of the organic electroluminescent device is measured to be reduced to 900 cd/m ² Is a time of (a) to be used. Comparative examples and application examples the electroluminescent properties of the devices are shown in table 2.

Table 2 example organic electroluminescent device performance table

Device embodiment numbering	Device numbering	On voltage/V	Luminescence peak position/nm	Maximum external quantum efficiency/%	1000cd/m ² Time external quantum efficiency/%	Half width/nm
							Comparative example 1	DD1	2.4	453	22.8	7.6	30
Comparative example 2	DD2	2.5	474	24.2	9.6	29
							Comparative example 3	DD3	2.8	476	18.6	13.7	36
Comparative example 4	DD4	2.9	481	16.3	12.4	35
							Example 1	D1	2.5	501	31.4	22.6	40
Example 2	D2	2.3	512	33.4	25.1	42
							Example 3	D3	2.4	508	30.8	22.8	43
Example 4	D4	2.5	509	33.2	24.1	44
							Example 5	D5	2.3	507	31.1	22.7	42
Example 6	D6	2.4	503	32.1	23.1	40
							Example 7	D7	2.3	505	33.6	24.8	42
Example 8	D8	2.5	510	30.6	22.3	43
							Example 9	D9	2.5	542	33.4	27.2	40
Example 10	D10	2.3	519	33.6	24.5	42
							Example 11	D11	2.3	538	31.1	25.2	45
Example 12	D12	2.5	520	33.5	25.5	44
							Example 13	D13	2.5	552	31.5	27.1	41
Example 14	D14	2.4	525	34.1	25.6	40
							Example 15	D15	2.3	512	31.2	24.1	39
Example 16	D16	2.3	518	31.3	24.3	43
							Example 17	D17	2.4	518	32.4	24.2	40
Example 18	D18	2.3	559	34.2	28.4	45
							Example 19	D19	2.3	529	33.8	30.5	44
Example 20	D20	2.3	537	34.2	26.7	40
							Example 22	D21	2.5	532	33.5	26.8	41
Example 22	D22	2.5	563	31.2	24.1	42
							Example 23	D23	2.4	534	34.5	31.1	40
Example 24	D24	2.3	571	34.3	28.8	44
							Example 25	D25	2.5	543	33.1	25.2	42
Example 26	D26	2.5	511	33.8	28.4	41
							Example 27	D27	2.3	516	34.0	27.8	42
Example 28	D28	2.5	507	31.2	22.6	44
							Example 29	D29	2.3	510	32.6	23.8	42
Example 30	D30	2.4	513	31.8	22.8	43
							Example 31	D31	2.4	503	33.9	25.1	40
Example 32	D32	2.3	515	32.0	23.4	43
							Example 33	D33	2.3	529	31.2	23.1	41
Example 34	D34	2.5	514	33.5	25.1	44
							Example 35	D35	2.5	547	31.3	25.7	40
Example 36	D36	2.4	521	33.9	25.1	41
							Example 37	D37	2.3	526	33.9	28.5	40
Example 38	D38	2.5	531	34.1	25.9	42
							Example 39	D39	2.3	522	30.6	23.2	43
Example 40	D40	2.3	562	32.1	26.7	43
							Example 41	D41	2.4	537	31.5	24.3	42
Example 42	D42	2.3	571	32.8	27.2	40
							Example 43	D43	2.3	533	34.1	28.3	41
Example 44	D44	2.3	551	34.3	31.4	41
							Example 45	D45	2.5	524	33.4	25.4	40
Example 46	D46	2.3	523	32.5	27.0	42
							Example 47	D47	2.4	520	33.6	25.2	40

The experimental data show that the compound greatly enriches a material system of multiple resonance-thermal activation delayed fluorescence by changing the central ring structure of the conjugated skeleton of the classical MR-TADF material, obviously reduces roll-off of a device taking the compound as an object, improves efficiency, easily realizes light emission exceeding 500 nm, and has good application prospect.

While the invention has been described in connection with the embodiments, it is not limited to the above embodiments, but it should be understood that various modifications and improvements can be made by those skilled in the art under the guidance of the inventive concept, and the scope of the invention is outlined in the appended claims.

It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.

Claims

1. The boron-nitrogen-containing polycyclic aromatic hydrocarbon based on five-membered heterocyclic ring structure is characterized in that the boron-nitrogen-containing polycyclic aromatic hydrocarbon is shown in any one of the following structures:

wherein X is a direct bond, O, S, se,* Represents a bond to two benzene rings;

y is O or S;

R ₅ is H,

2. The boron-nitrogen-containing polycyclic aromatic hydrocarbon according to claim 1, wherein it is represented by any one of the following structures:

/>

3. a method for producing a boron-nitrogen-containing polycyclic aromatic hydrocarbon based on a five-membered heterocyclic structure according to claim 2, comprising the steps of:

bromine-substituted furan or thiophene and a nitrogen-containing heterocyclic compound are taken as raw materials, cesium carbonate, tris (dibenzylideneacetone) dipalladium, tri-tert-butylphosphine and solvent o-xylene are added into the raw materials, and the raw materials react to prepare an intermediate;

Adding tert-butyllithium into a tert-butylbenzene solution of the intermediate, then adding boron tribromide, then adding N, N-diisopropylethylamine, and reacting to obtain the boron-nitrogen-containing polycyclic aromatic hydrocarbon based on the five-membered heterocyclic structure;

the structural formula of the nitrogen-containing heterocyclic compound is one or two of the following structures:

or the preparation method comprises the following steps:

adding phenylboronic acid or p-tert-butylphenylboronic acid, potassium carbonate, tetraphenylphosphine palladium, tetrahydrofuran and water into bromine-substituted furan or thiophene, and reacting to obtain an intermediate A;

adding a nitrogen-containing heterocyclic compound, cesium carbonate, tris (dibenzylideneacetone) dipalladium, tri-tert-butylphosphine and a solvent o-xylene into the intermediate A, and reacting to obtain an intermediate B;

adding tert-butyllithium into a tert-butylbenzene solution of the intermediate B, then adding boron tribromide, then adding N, N-diisopropylethylamine, and reacting to obtain the boron-nitrogen-containing polycyclic aromatic hydrocarbon based on the five-membered heterocyclic structure;

4. use of the boron-nitrogen-containing polycyclic aromatic hydrocarbon based on five-membered heterocyclic structure according to claim 1 or 2 in the preparation of organic electroluminescent devices.

5. The use of the boron-nitrogen-containing polycyclic aromatic hydrocarbon based on a five-membered heterocyclic structure according to claim 4 for the preparation of an organic electroluminescent device, wherein the boron-nitrogen-containing polycyclic aromatic hydrocarbon based on a five-membered heterocyclic structure according to claim 1 or 2 is used as a material of a light emitting layer of the organic electroluminescent device.