# US 11,993,617 B2 · Organic luminescent material having an ancillary ligand with a partially fluorine-substituted substituent > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,993,617 B2 - Document ID: US11993617B2 - Status: Granted - Kind: B2 - Application number: 17/071,612 - Filed: 2020-10-15 - Published: 2021-04-22 - Granted: 2024-05-28 - Earliest claimed: 2019-10-18 - Assignees: Beijing Summer Sprout Technology Co., Ltd. - Applicants: Beijing Summer Sprout Technology Co., Ltd. - Inventors: Zhihong Dai; Yongjun Wu; Jin Qiao; Chi Yuen Raymond Kwong; Chuanjun Xia - Web page: https://patentgrep.com/patent/US11993617B2 ## CPC - C07F 3/06: Zinc compounds - C07F 15/0033: {Iridium compounds} - H10K 85/342: {comprising iridium} - H10K 50/11: characterised by the electroluminescent [EL] layers - H10K 2101/10: Triplet emission - C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22) - H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES ## Abstract Provided is an organic light-emitting material having an ancillary ligand with partially fluorinated substituents. The organic light-emitting material is a metal complex having a diketone ancillary ligand with partially fluorinated substituents and may be used as a light-emitting material in an organic electroluminescent device. These new types of metal complex can fine-tune the emission wavelength more effectively, reduce voltage, improve efficiency, prolong lifetimes, and provide better device performance. Further provided are an organic electroluminescent device and a compound formulation. ## Claims ### Claim 1 A metal complex, wherein the metal complex has a structure represented by Formula M(La)u(Lb)v(Lc)w; wherein the metal M is selected from the group consisting of Cu, Ag, Au, Ru, Rh, Pd, Os, Ir, and Pt; wherein La, Lb, and Lc can be optionally joined to form a multi-dentate ligand; wherein u=1 or 2, v=1 or 2, w=0 or 1, and u+v+w=3; when u=2, two La may be identical or different; when v=2, two Lb may be identical or different; wherein La with a structure represented by Formula 1: wherein A is, at each occurrence identically or differently, selected from O, S, Se, or NR3; wherein x1=0, 1, 2, or 3, y1=0, 1, 2, or 3, and x1+y1=3; wherein x2=0, 1, 2, or 3, y2=0, 1, 2, or 3, and x2+y2=3; wherein x3=0 or 1, y3=0 or 1, and x3+y3=1; wherein y1+y2+y3≥1; wherein R1 and R3 are, at each occurrence identically or differently, selected from the group consisting of hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof; and when R1 and R3 are selected from the above substituted groups, the substitution is selected from the group consisting of deuterium, unsubstituted alkyl having 1 to 20 carbon atoms, unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, unsubstituted heteroalkyl having 1 to 20 carbon atoms, unsubstituted alkoxy having 1 to 20 carbon atoms, unsubstituted alkenyl having 2 to 20 carbon atoms, unsubstituted alkylsilyl having 3 to 20 carbon atoms, unsubstituted amino having 0 to 20 carbon atoms, a cyano group, an isocyano group, and combinations thereof; wherein R2 is, at each occurrence identically or differently, selected from -L-C(F)m(R)n, and L is, at each occurrence identically or differently, selected from a single bond, substituted or unsubstituted alkylene having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkylene having 3 to 20 ring carbon atoms; and when L is selected from the above substituted groups, the substitution is selected from the group consisting of deuterium, unsubstituted alkyl having 1 to 20 carbon atoms, unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, unsubstituted heteroalkyl having 1 to 20 carbon atoms, unsubstituted alkoxy having 1 to 20 carbon atoms, unsubstituted alkenyl having 2 to 20 carbon atoms, unsubstituted alkylsilyl having 3 to 20 carbon atoms, unsubstituted amino having 0 to 20 carbon atoms, a cyano group, an isocyano group, and combinations thereof; wherein m=1 or 2, n=1 or 2, and m+n=3; when n=2, two R may be identical or different; wherein R is, at each occurrence identically or differently, selected from the group consisting of hydrogen, deuterium, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof; and when R is selected from the above substituted groups, the substitution is selected from the group consisting of unsubstituted alkyl having 1 to 20 carbon atoms, unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, unsubstituted heteroalkyl having 1 to 20 carbon atoms, unsubstituted alkoxy having 1 to 20 carbon atoms, unsubstituted alkenyl having 2 to 20 carbon atoms, and unsubstituted alkylsilyl having 3 to 20 carbon atoms; wherein adjacent substituents R1 can be optionally joined to form a ring; wherein Lb and Lc are, at each occurrence identically or differently, selected from the group consisting of structures represented by Formula 2, Formula 3, or Formula 4: wherein Ra and Rb each represent mono-substitution, multiple-substitutions, or non-substitution; wherein substituents Ra and Rb are, at each occurrence identically or differently, selected from the group consisting of hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof, wherein none of adjacent substituents Ra and Rb in Formula 2, Formula 3, and Formula 4 are joined to form a ring. ### Claim 2 (depends on 1) The metal complex of claim 1, wherein the metal is selected from the group consisting of Ir and Pt. ### Claim 3 (depends on 1) The metal complex of claim 1, wherein L is selected from a single bond, substituted or unsubstituted alkylene having 1 to 20 carbon atoms, or substituted or unsubstituted cycloalkylene having 3 to 20 ring carbon atoms. ### Claim 4 (depends on 1) The metal complex of claim 1, wherein R is selected from hydrogen, deuterium, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, or substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms. ### Claim 5 (depends on 1) The metal complex of claim 1, wherein R2 is, at each occurrence identically or differently, selected from -L-C(F)m(R)n, wherein m is 2. ### Claim 6 (depends on 1) The metal complex of claim 1, wherein R1 and R3 are, at each occurrence identically or differently, selected from the group consisting of hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, and combinations thereof; and adjacent substituents R1 can be optionally joined to form a ring. ### Claim 7 (depends on 1) The metal complex of claim 1, wherein y1 is 1, y2 is 0, and y3 is 0; y1 is 1, y2 is 1, and y3 is 0; y1 is 0, y2 is 0, and y3 is 1; y1 is 2, y2 is 0, and y3 is 0; y1 is 2, y2 is 1, and y3 is 0; or y1 is 2, y2 is 2, and y3 is 0. ### Claim 8 (depends on 1) The metal complex of claim 1, wherein La is selected from the group consisting of the following structures: ### Claim 9 (depends on 8) The metal complex of claim 8, wherein the ligand Lb is, at each occurrence identically or differently, selected from the group consisting of Lb1 to Lb162, Lb201 to Lb210, Lb215 to Lb222 and deuterides of Lb1 to Lb162, Lb201 to Lb210, Lb215 to Lb222: wherein TMS is trimethylsilyl. ### Claim 10 (depends on 9) The metal complex of claim 9, wherein hydrogens in the ligands La, Lb and Lc can be partially or fully deuterated. ### Claim 11 (depends on 9) The metal complex of claim 9, wherein the metal complex has a structure of Ir(La)(Lb)2, wherein La is selected from the group consisting of La1 to La1123 and La1126 to La1189, and Lb is, at each occurrence identically or differently, selected from the group consisting of Lb1 to Lb162, Lb201 to Lb210, Lb215 to Lb222 and deuterides of Lb1 to Lb162, Lb201 to Lb210, Lb215 to Lb222. ### Claim 12 (depends on 9) The metal complex of claim 9, wherein the metal complex has a structure of Ir(La)(Lb)2, wherein two Lb are identical, and La and Lb respectively correspond to structures listed in the following table: Compound La Lb Compound La Lb 1 La103 Lb3 2 La103 Lb6 3 La334 Lb3 4 La334 Lb6 5 La433 Lb3 6 La433 Lb6 7 La499 Lb3 8 La499 Lb6 9 La565 Lb3 10 La565 Lb6 11 La598 Lb3 12 La598 Lb6 13 La631 Lb3 14 La631 Lb6 15 La829 Lb3 16 La829 Lb6 17 La991 Lb3 18 La991 Lb6 19 La1010 Lb3 20 La1010 Lb6 21 La103 Lb18 22 La103 Lb21 23 La334 Lb18 24 La334 Lb21 25 La433 Lb18 26 La433 Lb21 27 La499 Lb18 28 La499 Lb21 29 La565 Lb18 30 La565 Lb21 31 La598 Lb18 32 La598 Lb21 33 La631 Lb18 34 La631 Lb21 35 La829 Lb18 36 La829 Lb21 37 La991 Lb18 38 La991 Lb21 39 La1010 Lb18 40 La1010 Lb21 41 La103 Lb24 42 La103 Lb27 43 La334 Lb24 44 La334 Lb27 45 La433 Lb24 46 La433 Lb27 47 La499 Lb24 48 La499 Lb27 49 La565 Lb24 50 La565 Lb27 51 La598 Lb24 52 La598 Lb27 53 La631 Lb24 54 La631 Lb27 55 La829 Lb24 56 La829 Lb27 57 La991 Lb24 58 La991 Lb27 59 La1010 Lb24 60 La1010 Lb27 61 La103 Lb30 62 La103 Lb42 63 La334 Lb30 64 La334 Lb42 65 La433 Lb30 66 La433 Lb42 67 La499 Lb30 68 La499 Lb42 69 La565 Lb30 70 La565 Lb42 71 La598 Lb30 72 La598 Lb42 73 La631 Lb30 74 La631 Lb42 75 La829 Lb30 76 La829 Lb42 77 La991 Lb30 78 La991 Lb42 79 La1010 Lb30 80 La1010 Lb42 81 La103 Lb54 82 La103 Lb66 83 La334 Lb54 84 La334 Lb66 85 La433 Lb54 86 La433 Lb66 87 La499 Lb54 88 La499 Lb66 89 La565 Lb54 90 La565 Lb66 91 La598 Lb54 92 La598 Lb66 93 La631 Lb54 94 La631 Lb66 95 La829 Lb54 96 La829 Lb66 97 La991 Lb54 98 La991 Lb66 99 La1010 Lb54 100 La1010 Lb66 101 La103 Lb135 102 La103 Lb138 103 La334 Lb135 104 La334 Lb138 105 La433 Lb135 106 La433 Lb138 107 La499 Lb135 108 La499 Lb138 109 La565 Lb135 110 La565 Lb138 111 La598 Lb135 112 La598 Lb138 113 La631 Lb135 114 La631 Lb138 115 La829 Lb135 116 La829 Lb138 117 La991 Lb135 118 La991 Lb138 119 La1010 Lb135 120 La1010 Lb138 121 La103 Lb141 122 La103 Lb144 123 La334 Lb141 124 La334 Lb144 125 La433 Lb141 126 La433 Lb144 127 La499 Lb141 128 La499 Lb144 129 La565 Lb141 130 La565 Lb144 131 La598 Lb141 132 La598 Lb144 133 La631 Lb141 134 La631 Lb144 135 La829 Lb141 136 La829 Lb144 137 La991 Lb141 138 La991 Lb144 139 La1010 Lb141 140 La1010 Lb144 162 La103 Lb201 164 La334 Lb201 166 La433 Lb201 168 La499 Lb201 170 La565 Lb201 172 La598 Lb201 174 La631 Lb201 176 La829 Lb201 178 La991 Lb201 180 La1010 Lb201 181 La103 Lb202 182 La103 Lb203 183 La334 Lb202 184 La334 Lb203 185 La433 Lb202 186 La433 Lb203 187 La499 Lb202 188 La499 Lb203 189 La565 Lb202 190 La565 Lb203 191 La598 Lb202 192 La598 Lb203 193 La631 Lb202 194 La631 Lb203 195 La829 Lb202 196 La829 Lb203 197 La991 Lb202 198 La991 Lb203 199 La1010 Lb202 200 La1010 Lb203 201 La1133 Lb3 202 La1133 Lb6 203 La1133 Lb18 204 La1133 Lb21 205 La1133 Lb24 206 La1133 Lb27 207 La1133 Lb30 208 La1133 Lb42 209 La1133 Lb54 210 La1133 Lb66 211 La1133 Lb135 212 La1133 Lb138 213 La1133 Lb141 214 La1133 Lb144 218 La1133 Lb201 219 La1133 Lb202 220 La1133 Lb203 221 La1148 Lb3 222 La1148 Lb6 223 La1148 Lb18 224 La1148 Lb21 225 La1148 Lb24 226 La1148 Lb27 227 La1148 Lb30 228 La1148 Lb42 229 La1148 Lb54 230 La1148 Lb66 231 La1148 Lb135 232 La1148 Lb138 233 La1148 Lb141 234 La1148 Lb144 238 La1148 Lb201 239 La1148 Lb202 240 La1148 Lb203 241 La103 Lb209 242 La103 Lb215 243 La334 Lb209 244 La334 Lb215 245 La433 Lb209 246 La433 Lb215 247 La499 Lb209 248 La499 Lb215 249 La565 Lb209 250 La565 Lb215 251 La598 Lb209 252 La598 Lb215 253 La631 Lb209 254 La631 Lb215 255 La829 Lb209 256 La829 Lb215 257 La991 Lb209 258 La991 Lb215 259 La1010 Lb209 260 La1010 Lb215 261 La103 Lb216 262 La103 Lb217 263 La334 Lb216 264 La334 Lb217 265 La433 Lb216 266 La433 Lb217 267 La499 Lb216 268 La499 Lb217 269 La565 Lb216 270 La565 Lb217 271 La598 Lb216 272 La598 Lb217 273 La631 Lb216 274 La631 Lb217 275 La829 Lb216 276 La829 Lb217 277 La991 Lb216 278 La991 Lb217 279 La1010 Lb216 280 La1010 Lb217 281 La103 Lb218 282 La103 Lb219 283 La334 Lb218 284 La334 Lb219 285 La433 Lb218 286 La433 Lb219 287 La499 Lb218 288 La499 Lb219 289 La565 Lb218 290 La565 Lb219 291 La598 Lb218 292 La598 Lb219 293 La631 Lb218 294 La631 Lb219 295 La829 Lb218 296 La829 Lb219 297 La991 Lb218 298 La991 Lb219 299 La1010 Lb218 300 La1010 Lb219 301 La103 Lb220 302 La103 Lb221 303 La334 Lb220 304 La334 Lb221 305 La433 Lb220 306 La433 Lb221 307 La499 Lb220 308 La499 Lb221 309 La565 Lb220 310 La565 Lb221 311 La598 Lb220 312 La598 Lb221 313 La631 Lb220 314 La631 Lb221 315 La829 Lb220 316 La829 Lb221 317 La991 Lb220 318 La991 Lb221 319 La1010 Lb220 320 La1010 Lb221 321 La103 Lb222 322 La598 Lb222 323 La334 Lb222 324 La631 Lb222 325 La433 Lb222 326 La829 Lb222 327 La499 Lb222 328 La991 Lb222 329 La565 Lb222 330 La1010 Lb222. ### Claim 13 (depends on 9) The metal complex of claim 9, wherein the metal complex has a structure of Ir(La)(Lb)2, wherein two Lb are different, and La and Lb respectively correspond to structures listed in the following table: Compound La Lb Lb Compound La Lb Lb 331 La433 Lb135 Lb215 332 La499 Lb135 Lb215 333 La565 Lb135 Lb215 334 La598 Lb135 Lb215 335 La631 Lb135 Lb215 336 La433 Lb135 Lb216 337 La499 Lb135 Lb216 338 La565 Lb135 Lb216 339 La598 Lb135 Lb216 340 La631 Lb135 Lb216 341 La433 Lb144 Lb217 342 La499 Lb144 Lb217 343 La565 Lb144 Lb217 344 La598 Lb144 Lb217 345 La631 Lb144 Lb217 346 La433 Lb144 Lb218 347 La499 Lb144 Lb218 348 La565 Lb144 Lb218 349 La598 Lb144 Lb218 350 La631 Lb144 Lb218 351 La433 Lb215 Lb216 352 La499 Lb215 Lb216 353 La565 Lb215 Lb216 354 La598 Lb215 Lb216 355 La631 Lb215 Lb216 356 La433 Lb219 Lb220 357 La499 Lb219 Lb220 358 La565 Lb219 Lb220 359 La598 Lb219 Lb220 360 La631 Lb219 Lb220 361 La433 Lb138 Lb219 362 La499 Lb138 Lb219 363 La565 Lb138 Lb219 364 La598 Lb138 Lb219 365 La631 Lb138 Lb219 366 La433 Lb138 Lb220 367 La499 Lb138 Lb220 368 La565 Lb138 Lb220 369 La598 Lb138 Lb220 370 La631 Lb138 Lb220 371 La433 Lb209 Lb221 372 La499 Lb209 Lb221 373 La565 Lb209 Lb221 374 La598 Lb209 Lb221 375 La631 Lb209 Lb221 376 La433 Lb209 Lb222 377 La499 Lb209 Lb222 378 La565 Lb209 Lb222 379 La598 Lb209 Lb222 380 La631 Lb209 Lb222 381 La433 Lb217 Lb218 382 La499 Lb217 Lb218 383 La565 Lb217 Lb218 384 La598 Lb217 Lb218 385 La631 Lb217 Lb218 386 La433 Lb220 Lb221 387 La499 Lb220 Lb221 388 La565 Lb220 Lb221 389 La598 Lb220 Lb221 390 La631 Lb220 Lb221. ### Claim 14 (depends on 1) An electroluminescent device, comprising: an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises the metal complex according to claim 1. ### Claim 15 (depends on 14) The device of claim 14, wherein the organic layer is a light-emitting layer, and the metal complex is a light-emitting material. ### Claim 16 (depends on 14) The device of claim 14, wherein the device emits red light or white light. ### Claim 17 (depends on 15) The device of claim 15, wherein the organic layer further comprises at least one host material, and the host material comprises at least one chemical group selected from the group consisting of benzene, pyridine, pyrimidine, triazine, carbazole, azacarbazole, indolocarbazole, dibenzothiophene, aza-dibenzothiophene, dibenzofuran, azadibenzofuran, dibenzoselenophene, triphenylene, azatriphenylene, fluorene, silafluorene, naphthalene, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene, azaphenanthrene, and combinations thereof. ### Claim 18 (depends on 1) A compound formulation, comprising the metal complex of claim 1. ### Claim 19 (depends on 1) The metal complex of claim 1, wherein L is selected from the group consisting of a single bond, methylene, and ethylene. ### Claim 20 (depends on 1) The metal complex of claim 1, wherein R is selected from the group consisting of hydrogen, deuterium, methyl, ethyl, and propyl. ### Claim 21 (depends on 1) The metal complex of claim 1, R1 and R3 are, at each occurrence identically or differently, selected from the group consisting of hydrogen, deuterium, fluorine, methyl, ethyl, propyl, butyl, cyclopropyl, 3-methylbutyl, 3-ethylpentyl, trifluoromethyl, 2,2,2-trifluoroethyl, trimethylsilyl, dimethylisopropylsilyl, and combinations thereof, and adjacent substituents R1 can be optionally joined to form a ring.