CN111072695B - 一种含硼氮杂萘的有机小分子材料及其制备方法与应用 - Google Patents
一种含硼氮杂萘的有机小分子材料及其制备方法与应用 Download PDFInfo
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- CN111072695B CN111072695B CN201911249641.XA CN201911249641A CN111072695B CN 111072695 B CN111072695 B CN 111072695B CN 201911249641 A CN201911249641 A CN 201911249641A CN 111072695 B CN111072695 B CN 111072695B
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- 229910052796 boron Inorganic materials 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 8
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- 150000003384 small molecules Chemical class 0.000 claims description 8
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- 239000002904 solvent Substances 0.000 abstract description 16
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- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 34
- 238000005481 NMR spectroscopy Methods 0.000 description 34
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- 238000006243 chemical reaction Methods 0.000 description 24
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- 238000001228 spectrum Methods 0.000 description 17
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- 239000001257 hydrogen Substances 0.000 description 16
- 229910052739 hydrogen Inorganic materials 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 12
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 description 12
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 12
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- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 description 8
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- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 7
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- 229910052763 palladium Inorganic materials 0.000 description 6
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 6
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- 150000004982 aromatic amines Chemical class 0.000 description 5
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- 239000007788 liquid Substances 0.000 description 4
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 4
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- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 description 3
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 description 3
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- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- -1 boric acid ester Chemical class 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 229940125898 compound 5 Drugs 0.000 description 3
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- LZJHACNNMBYMSO-UHFFFAOYSA-N 1,1-dimethyl-3-propylurea Chemical compound CCCNC(=O)N(C)C LZJHACNNMBYMSO-UHFFFAOYSA-N 0.000 description 2
- BKPDQETYXNGMRE-UHFFFAOYSA-N 1-tert-butyl-9h-carbazole Chemical compound N1C2=CC=CC=C2C2=C1C(C(C)(C)C)=CC=C2 BKPDQETYXNGMRE-UHFFFAOYSA-N 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 description 2
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 2
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- MHJCZOMOUCUAOI-UHFFFAOYSA-N n-tert-butyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(C(C)(C)C)C1=CC=CC=C1 MHJCZOMOUCUAOI-UHFFFAOYSA-N 0.000 description 2
- 229950000688 phenothiazine Drugs 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 description 1
- 244000286893 Aspalathus contaminatus Species 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- GSVAFVMURLKGLG-UHFFFAOYSA-N azaborinino[1,2-a]azaborinine Chemical compound C1=CC=CN2C=CC=CB21 GSVAFVMURLKGLG-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- PNPBGYBHLCEVMK-UHFFFAOYSA-N benzylidene(dichloro)ruthenium;tricyclohexylphosphanium Chemical compound Cl[Ru](Cl)=CC1=CC=CC=C1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1 PNPBGYBHLCEVMK-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
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- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
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- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- DKHNGUNXLDCATP-UHFFFAOYSA-N dipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile Chemical compound C12=NC(C#N)=C(C#N)N=C2C2=NC(C#N)=C(C#N)N=C2C2=C1N=C(C#N)C(C#N)=N2 DKHNGUNXLDCATP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011984 grubbs catalyst Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000026045 iodination Effects 0.000 description 1
- 238000006192 iodination reaction Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- DQEUYIQDSMINEY-UHFFFAOYSA-M magnesium;prop-1-ene;bromide Chemical compound [Mg+2].[Br-].[CH2-]C=C DQEUYIQDSMINEY-UHFFFAOYSA-M 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- VGGNVBNNVSIGKG-UHFFFAOYSA-N n,n,2-trimethylaziridine-1-carboxamide Chemical compound CC1CN1C(=O)N(C)C VGGNVBNNVSIGKG-UHFFFAOYSA-N 0.000 description 1
- VKSWIFGDKIEVFZ-UHFFFAOYSA-N n,n-diphenyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C(N(C=2C=CC=CC=2)C=2C=CC=CC=2)C=C1 VKSWIFGDKIEVFZ-UHFFFAOYSA-N 0.000 description 1
- ZTLUNQYQSIQSFK-UHFFFAOYSA-N n-[4-(4-aminophenyl)phenyl]naphthalen-1-amine Chemical compound C1=CC(N)=CC=C1C(C=C1)=CC=C1NC1=CC=CC2=CC=CC=C12 ZTLUNQYQSIQSFK-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- ORFSSYGWXNGVFB-UHFFFAOYSA-N sodium 4-amino-6-[[4-[4-[(8-amino-1-hydroxy-5,7-disulfonaphthalen-2-yl)diazenyl]-3-methoxyphenyl]-2-methoxyphenyl]diazenyl]-5-hydroxynaphthalene-1,3-disulfonic acid Chemical compound COC1=C(C=CC(=C1)C2=CC(=C(C=C2)N=NC3=C(C4=C(C=C3)C(=CC(=C4N)S(=O)(=O)O)S(=O)(=O)O)O)OC)N=NC5=C(C6=C(C=C5)C(=CC(=C6N)S(=O)(=O)O)S(=O)(=O)O)O.[Na+] ORFSSYGWXNGVFB-UHFFFAOYSA-N 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
- H10K85/322—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising boron
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
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Abstract
本发明公开了一种含硼氮杂萘的有机小分子材料及其制备方法与应用。该有机小分子材料以含硼氮杂萘核为骨架单元,通过改变其两侧连接单元及其数量,可以调节材料的分子量、π共轭性及分子内电荷转移的性质,具有式(1)或式(2)所示的结构。该有机小分子材料结构单一,分子量确定;在常用溶剂中具有较好的溶解性及成膜性;可应用于有机电致发光二极管。此类该有机小分子材料能有效地解决单极性发光材料载流子不平衡的问题,从而简化器件结构并且提高了器件的性能。
Description
技术领域
本发明属于电致发光材料技术领域,具体涉及一种含硼氮杂萘的有机小分子材料及其制备方法与应用。
背景技术
有机电致发光二极管(OLED)因具有高效、低电压驱动,易于大面积制备及全色显示等优点具有广阔的应用前景,得到人们的广泛关注。该研究始于上个世纪50年代,直到1987年美国柯达公司的邓青云博士等在专利US4356429中采用三明治器件结构,研制出的OLED器件在10V直流电压驱动下发光亮度达到1000cd/m2,使OLED获得了划时代的发展。在过去的二十年里,采用新型发光体,尤其是有机-重金属配合物膦光发射体的OLED器件取得了不小的成功。然而,由于较难获得能带隙膦光体,目前能够满足高效纯蓝色发光(yCIE<0.15,yCIE+xCIE<0.30)的膦光发射体数量十分稀少,并且相对于绿色和红色膦光材料,要选择针对蓝色膦光的具有高三线态能的主体材料也具有相当的挑战性。因此,开发蓝色膦光材料的主体材料具有非常急迫的实际应用需求。目前,开发具有双极性的具有较小单线态-三线态能级差的主体材料,成为设计高效低滚降的主体材料具有重要的意义。同时,发展高效、稳定的蓝色荧光发光体仍然十分必要。考虑到多方面的因素,采用蓝色荧光材料可以使OLED全彩显示或者白光照明的实用化生产降低成本以及简化制造工序。但是以往经典的蓝色有机荧光材料从分子结构上可以划分为n-型分子,-型分子,他们在器件工作中要么表现为电子主导,要么表现为空穴主导,因而难以实现载流子的平衡,从而导致器件电流效率和量子效率偏低。而简单的设计Donor-Acceptor(D-A)型分子,虽然可能实现双极性传输,达到平衡载流子的目的,但是由于给电子单元和亲电子单元之间的分子内电荷转移作用,会使得化合物的带隙变窄,导致发光峰红移,难以获得理想的蓝色发光。要克服这一困难,必须的选择具有合适强度给电性的给体和亲电性的受体组合成分子,把分子内电荷转移控制在一定的程度内,才能获得性能好,色纯度高的蓝色有机荧光材料。
截止目前,用于有机光电器件的绝大多数的蒸镀分子的骨架为硫氧芴、膦氧、三苯胺等单元为核,而以硼氮杂萘为核的有机发光小分子却鲜有报道。
至今有机发光二极管已经取得了长足的进展,通过荧光膦光杂化,我们可以获得器件结构简单效率很高的白光器件。而这种荧光膦光杂化器件的效率很大程度上依赖于荧光的效率,因此发展高效的荧光材料依然具有举足轻重的意义。基于此,我们开发了一系列具有新颖结构易于合成的荧光发光材料。
发明内容
为解决现有技术的缺点和不足之处,本发明的首要目的在于提供一种含硼氮杂萘的有机小分子材料。该材料结构单一,分子量确定,具有较好的溶解性及成膜性。
本发明的另一目的在于提供上述含硼氮杂萘的有机小分子材料的制备方法。
本发明的再一目的在于提供上述含硼氮杂萘的有机小分子材料的应用。
本发明目的通过以下技术方案实现:
一种含硼氮杂萘的有机小分子材料,其具有如下式(1)或式(2)所示的结构:
优选的,式(2)中的Ar可以相同,也可以不同。
优选的,所述含硼氮杂萘的有机小分子材料的结构式如下:
上述含硼氮杂萘的有机小分子材料的制备方法,包括以下步骤:
(1)制备中间体:将二烯丙基胺(Diallylamine)通过成环得到硼氮杂环([1,2]azaborinino[1,2-a][1,2]azaborinine),然后通过溴化、氯化或者碘化,得到不同的反应活性位点,即获得中间体;
(2)将步骤(1)制得的中间体通过Suzuki偶联、Buchwald-Hartwig偶联或者铜催化卤代芳烃氨基化反应,制得所述含硼氮杂萘的有机小分子材料。
进一步的,所述中间体为如下结构之一:
进一步的,所述Suzuki偶联反应是将中间体和硼酸酯或者硼酸原料,与反应溶剂、碱溶液以及催化剂混合后,在气体保护下,于90-100℃加热反应18-24小时。
具体的,所述Suzuki偶联反应的具体步骤为:将中间体和硼酸酯或者硼酸原料在甲苯、乙醇、碳酸钾水溶液、四(三苯基膦)钯膦零价钯的反应瓶中,通氮气半小时,90-100℃加热反应18-24小时,过硅胶色谱柱提纯并进一步升华提纯。
进一步的,所述Buchwald-Hartwig偶联反应是将中间体、含芳香胺给体单元、反应溶剂、催化剂和碱混合后,加热回流下搅拌反应24小时。
具体的,所述Buchwald-Hartwig偶联反应的具体步骤为:将中间体和含芳香胺给体单元、甲苯、醋酸钯、三叔丁基膦和碳酸钾在反应瓶中加热回流下搅拌反应24小时,过硅胶色谱柱提纯并进一步升华提纯。
进一步的,所述铜催化卤代芳烃氨基化反应是将中间体、含芳香胺给体单元、碱、18-冠醚-6和反应溶剂混合后,加热180℃过夜。
具体的,所述铜催化卤代芳烃氨基化反应的具体步骤为:将中间体及含芳香胺给体单元、CuI、K2CO3、18-冠醚-6溶于DMPU(N,N-二甲基丙烯基脲)中,加热180℃过夜,过硅胶色谱柱提纯并进一步升华提纯。
进一步的,所述含芳香胺给体单元包括咔唑、叔丁基咔唑、吖啶、吩噁嗪、吩噻嗪、二苯胺或叔丁基二苯胺。
上述含硼氮杂萘的有机小分子材料可应用于包括有机发光二极管等有机光电器件中。
一种有机电致发光器件,包括基板、依次在基板上形成的阳极层、发光层单元和阴极层;所述的发光层单元包括空穴注入层、空穴传输层、一个以上的发光层和电子传输层,所述的空穴传输层与所述的电子传输层之间为一个以上的发光层,其特征在于:所述的发光层材料为上述含硼氮杂萘的有机小分子材料的任意一种化合物或两种以上化合物的混合。
与现有技术相比,本发明具有以下优点及有益效果:
(1)本发明提供的含硼氮杂萘的有机小分子材料结构单一,分子量确定,便于提纯,多次合成再现性好,且便于研究结构-性能的关系;
(2)本发明提供的含硼氮杂萘的有机小分子材料具有较低的生化温度和分解温度,薄膜形态稳定;在常用溶剂中具有较好的溶解性及成膜性;
(3)通过改变连接的化学结构可以有效地调控该有机小分子材料的共轭长度和发光的颜色;
(4)通过改变含芳香结构上的修饰基团,可进一步改善该有机小分子材料的物理特性以及基于其的光电器件性能;
(5)本发明提供的有机小分子材料能有效地解决单极性发光材料载流子不平衡的问题,从而简化器件结构并且提高了器件的性能。
具体实施方式
下面结合实施例对本发明作进一步详细的描述,但本发明的实施方式不限于此。本发明涉及的原料均可从市场上直接购买。对于未特别注明的工艺参数,可参照常规技术进行。
实施例1
化合物3的合成
将二烯丙基胺(Diallylamine)(25mmol),溶于150ml无水二氯甲烷中,冷却至-40℃,滴加入BCl3(30mmol),保温2小时后升温至室温,搅拌过夜。除去易挥发溶剂,得到白色液体(10.0g,产率50%)。将白色液体产物和250ml无水THF加入到三口圆底烧瓶中,冷却至-40℃,将烯丙基溴化镁(60ml,1.7mol/L)滴加进反应釜中,保温2小时后升温至室温,搅拌过夜。除去易挥发溶剂,用石油醚萃取,除去不溶物后,除去易挥发溶剂,减压蒸馏得到无色液体2(5.0g,产率60%)。将无色液体2溶解到无水二氯甲烷中,冷却至-40℃,将红褐色Grubbs催化剂((Cy3P)2Cl2Ru=CHPh)滴加进无色液体2中,保温1小时后升温至室温,搅拌过夜。除去易挥发溶剂,减压蒸馏得到产物化合物2。将化合物2与DDQ(2,3-二氯-5,6-二氰对苯醌)溶于正己烷中,加热60℃,搅拌一周,用正己烷洗涤产物,过凝胶色谱柱,得到白色固体化合物3。化合物3的核磁共振氢谱:1H NMR(300MHz,DMSO-d6):7.25(d,2H),6.93(d,2H),6.19(d,2H),5.00(d,2H)。
实施例2
将无水AlCl3(0.30mmol)与NBS(N-bromosuccinimide,N-溴代丁二酰亚胺)(0.30mmol)加入反应瓶中,将无水二氯甲烷加入到反应釜,搅拌半小时后冷却至-40℃。将化合物3(0.30mmol)的二氯甲烷溶液加入到反应釜中,搅拌2小时后升温至室温,搅拌过夜。用正己烷萃取,过柱,得到无色产物化合物4。化合物4的核磁共振氢谱:1H NMR(300MHz,DMSO-d6):δ7.70(s,1H),7.25(d,1H),6.93(d,2H),6.19(d,2H),5.00(d,1H)。
实施例3
将无水AlCl3(0.30mmol)与NCS(N-chlorosuccinimide,N-氯代丁二酰亚胺)(0.30mmol)加入反应瓶中,将无水二氯甲烷加入到反应釜,搅拌半小时后冷却至-40℃。将化合物3(0.30mmol)的二氯甲烷溶液加入到反应釜中,搅拌2小时后升温至室温,搅拌过夜。用正己烷萃取,过柱,得到无色产物化合物5。化合物5的核磁共振氢谱:1H NMR(300MHz,DMSO-d6):δ7.43(s,1H),7.25(d,1H),6.93(d,2H),6.19(d,2H),5.00(d,1H)。
实施例4
将无水AlBr3(0.70mmol)与NBS(N-bromosuccinimide)(0.70mmol)加入反应瓶中,将无水二氯甲烷加入到反应釜,搅拌半小时后冷却至-40℃。将化合物3(0.30mmol)的二氯甲烷溶液加入到反应釜中,搅拌2小时后升温至室温,搅拌过夜。用正己烷萃取,过柱,得到无色产物化合物6。化合物6的核磁共振氢谱:1H NMR(300MHz,DMSO-d6):δ7.70(s,2H),6.93(d,2H),6.19(d,2H)。
实施例5
将无水AlBr3(0.45mmol)与NCS(N-chlorosuccinimide,N-氯代丁二酰亚胺)(0.45mmol)加入反应瓶中,将无水二氯甲烷加入到反应釜,搅拌半小时后冷却至-40℃。将化合物5(0.30mmol)的二氯甲烷溶液加入到反应釜中,搅拌2小时后升温至室温,搅拌过夜。用正己烷萃取,过柱,得到无色产物化合物7。化合物7的核磁共振氢谱:1H NMR(300MHz,DMSO-d6):δ7.70(s,1H),7.43(s,1H),6.93(d,2H),6.19(d,2H)。
实施例6
M1的合成
将化合物4(3mmol),咔唑(3.3mmol),CuI(0.23g),K2CO3(0.55g),18-冠醚-6(0.1g)溶于DMPU(N,N-二甲基丙烯基脲)中,加热180℃,过夜,用二氯甲烷萃取,干燥,萃取,过柱得到0.76g化合物M1。产率83%。化合物M1的核磁共振氢谱:1H NMR(300MHz,DMSO-d6):δ8.55(d,1H),8.11(m,2H),7.58(m,1H),7.50(m,2H),7.36(m,1H),7.20-7.26(m,5H),6.96(d,1H),6.37(d,1H),6.19(d,1H),5.00(d,1H)。
实施例7
M2的合成
将化合物4(3mmol),叔丁基咔唑(3.3mmol),CuI(0.23g),K2CO3(0.55g),18-冠醚-6(0.1g)溶于DMPU中(N,N-二甲基丙烯基脲),加热180℃,过夜,用二氯甲烷萃取,干燥,萃取,过柱得到0.80g化合物M2。产率84%。化合物M2的核磁共振氢谱:1H NMR(300MHz,DMSO-d6):δ8.95(d,1H),8.36(m,2H),7.86(m,1H),7.62(m,2H),7.50(m,3H),7.25-7.10(m,2H),6.93(d,1H),6.37(d,1H),6.19(d,1H),5.00(d,1H),1.43(s,12H)。
实施例8
M3的合成
将化合物4(3mmol),吖啶(3.5mmol,0.72g),作为溶剂的100毫升甲苯,60毫克醋酸钯,三叔丁基膦膦(0.5mmol,0.11g)和0.75克碳酸钾在加热回流下搅拌反应24小时膦。冷却后,将混合液倒入200毫升水中,并用二氯甲烷萃取产物。无水硫酸镁干燥有机相,分离后去除溶剂,用硅胶色谱柱分离提纯得到白色固体,再经过干燥后于真空下升华得到高纯度产物(0.86g,产率86%)。化合物M3的核磁共振氢谱:1H NMR(300MHz,DMSO-d6):δ7.25-7.10(m,7H),6.95-6.93(m,4H),6.72(s,1H),6.19(d,2H),5.00(d,1H),1.69(s,6H)。
实施例9
M4的合成
将化合物4(3mmol),吩噁嗪(3.5mmol,0.68g),作为溶剂的100毫升甲苯,60毫克醋酸钯,三叔丁基膦(0.5mmol,0.11g)和0.75克碳酸钾在加热回流下搅拌反应24小时。冷却后,将混合液倒入200毫升水中,并用二氯甲烷萃取产物。无水硫酸镁干燥有机相,分离后去除溶剂,用硅胶色谱柱分离提纯得到白色固体,再经过干燥后于真空下升华得到高纯度产物(0.87g,产率90%)。化合物M4的核磁共振氢谱:1H NMR(300MHz,DMSO-d6):δ7.25(d,1H),7.15-7.14(m,2H),7.01-6.93(m,8H),6.72(s,1H),6.19(d,2H),5.01(d,1H)。
实施例10
M5的合成
将化合物4(3mmol),吩噻嗪(3.5mmol,0.68g),作为溶剂的100毫升甲苯,60毫克醋酸钯,三叔丁基膦(0.5mmol,0.11g)和0.75克碳酸钾在加热回流下搅拌反应24小时。冷却后,将混合液倒入200毫升水中,并用二氯甲烷萃取产物。无水硫酸镁干燥有机相,分离后去除溶剂,用硅胶色谱柱分离提纯得到白色固体,再经过干燥后于真空下升华得到高纯度产物(0.87g,产率86%)。化合物M5的核磁共振氢谱:1H NMR(300MHz,DMSO-d6):δ7.67(d,2H),7.25-7.51(m,7H),6.93(d,2H),6.72(s,1H),6.20(d,2H),5.01(d,1H)。
实施例11
M6的合成
将化合物4(3mmol),二苯胺(3.5mmol,0.68g),作为溶剂的100毫升甲苯,60毫克醋酸钯,三叔丁基膦(0.5mmol,0.11g)和0.75克碳酸钾在加热回流下搅拌反应24小时。冷却后,将混合液倒入200毫升水中,并用二氯甲烷萃取产物。无水硫酸镁干燥有机相,分离后去除溶剂,用硅胶色谱柱分离提纯得到白色固体,再经过干燥后于真空下升华得到高纯度产物(0.87g,产率86%)。化合物M6的核磁共振氢谱:1H NMR(300MHz,DMSO-d6):δ7.36-7.41(m,6H),7.25(m,1H),6.93-7.00(m,6H),6.72(s,1H),6.20(d,2H),5.01(d,1H)。
实施例12
M7的合成
将化合物4(3mmol),叔丁基二苯胺(3.5mmol,1.00g),作为溶剂的100毫升甲苯,60毫克醋酸钯,三叔丁基膦(0.5mmol,0.11g)和0.75克碳酸钾。加热回流下搅拌反应24小时。冷却后,将混合液倒入200毫升水中,并用二氯甲烷萃取产物。无水硫酸镁干燥有机相,分离后去除溶剂,用硅胶色谱柱分离提纯得到白色固体,再经过干燥后于真空下升华得到高纯度产物(1.09g,产率86%)。化合物M7的核磁共振氢谱:1H NMR(300MHz,DMSO-d6):δ7.25(d,1H),7.10-7.00(m,8H),6.91-6.6.93(m,2H),6.72(s,1H),6.20(d,2H),5.01(d,1H),1.33(s,18H)。
实施例13
M8的合成
将化合物4(6mmol)和N,N-二苯基-4-(4,4,5,5-四甲基-1,3,2-二氧杂戊硼烷-2-基)苯胺(2.6g 7mmol)加入到250ml单口烧瓶中,加入120ml甲苯、40ml乙醇和30ml 2mol/L的碳酸钾水溶液,然后加入100mg的四(三苯基膦)钯膦零价钯,通氮气半小时,置换出反应体系中的氧气,通氮气完毕密封,90-100℃加热反应18-24小时,降温,二氯甲烷萃取,有机相干燥,过硅胶色谱柱,产率90%。化合物M8的核磁共振氢谱:1H NMR(300MHz,DMSO-d6):δ7.85(s,1H),7.24-7.00(m,17H),6.37(d,1H),6.20(d,1H),5.01(d,1H)。
实施例14
M9的合成
将化合物4(6mmol)和对咔唑苯硼酸酯(2.6g,7mmol)加入到250ml单口烧瓶中,加入120ml甲苯、40ml乙醇和30ml 2mol/L的碳酸钾水溶液,然后加入100mg的四(三苯基膦)钯膦零价钯,通氮气半小时,置换出反应体系中的氧气,通氮气完毕密封,90-100℃加热反应18-24小时,降温,二氯甲烷萃取,有机相干燥,过硅胶色谱柱,产率90%。化合物M9的核磁共振氢谱:1H NMR(300MHz,DMSO-d6):δ8.55(d,1H),8.19(d,1H),7.94(d,1H),7.85(s,1H),7.58-7.48(m,4H),7.36(m,1H),7.25-7.17(m,4H),6.93(m,1H),6.37(s,1H),6.17(d,1H),5.01(d,1H)。
实施例15
M10的合成
将化合物6(6mmol)和4-三苯胺硼酸酯(5.2g,14mmol)加入到250ml单口烧瓶中,加入120ml甲苯、40ml乙醇和30ml 2mol/L的碳酸钾水溶液,然后加入100mg的四(三苯基膦)钯膦零价钯,通氮气半小时,置换出反应体系中的氧气,通氮气完毕密封,90-100℃加热反应18-24小时,降温,二氯甲烷萃取,有机相干燥,过硅胶色谱柱,产率90%。化合物M10的核磁共振氢谱:1H NMR(300MHz,DMSO-d6):δ7.85(s,2H),7.24-7.00(m,30H),6.37(d,2H)。
实施例16
将化合物6(6mmol)和对咔唑苯硼酸酯(5.2g,14mmol)加入到250ml单口烧瓶中,加入120ml甲苯、40ml乙醇和30ml 2mol/L的碳酸钾水溶液,然后加入100mg的四(三苯基膦)钯膦零价钯,通氮气半小时,置换出反应体系中的氧气,通氮气完毕密封,90-100℃加热反应18-24小时,降温,二氯甲烷萃取,有机相干燥,过硅胶色谱柱,产率90%。化合物M11的核磁共振氢谱:1H NMR(300MHz,DMSO-d6):δ8.55(d,2H),8.19(d,2H),7.94(d,2H),7.85(s,2H),7.68-7.70(m,4H),7.58-7.48(m,8H),7.36(m,2H),7.25-7.17(m,6H),6.37(m,2H)。
实施例17
将化合物7(5mmol)和对咔唑苯硼酸酯(5.2g,7mmol)加入到250ml单口烧瓶中,加入120ml甲苯、40ml乙醇和30ml 2mol/L的碳酸钾水溶液,然后加入100mg的四(三苯基膦)钯膦零价钯,通氮气半小时,置换出反应体系中的氧气,通氮气完毕密封,90-100℃加热反应18-24小时,降温,二氯甲烷萃取,有机相干燥,过硅胶色谱柱,将得到的化合物与4-三苯胺硼酸加入到250ml单口烧瓶中,加入120ml甲苯、40ml乙醇和30ml 2mol/L的碳酸钾水溶液,然后加入100mg的Pd2(dba)3,通氮气半小时,置换出反应体系中的氧气,通氮气完毕密封,90-100℃加热反应18-24小时,降温,二氯甲烷萃取,有机相干燥,过硅胶色谱柱,得到目标产物,产率70%。化合物M12的核磁共振氢谱:1H NMR(300MHz,DMSO-d6):δ7.85(m,1H),8.19(d,1H),7.94(d,1H),7.85(s,2H),7.68-7.70(m,2H),7.50-7.48(m,4H),7.36-7.17(m,20H),6.37(d,2H)。
实施例18:
有机发光二极管(OLED)器件的制备
ITO玻璃经过超声波清洗后,用氧-Plasma处理,ITO玻璃的方块电阻为10/cm^2。空穴注入层为HAT-CN,空穴传输层为NPB和TCTA,发光层采用上述实施例所制备的化合物,电子传输层使用TPBI。阴极电极采用LiF/Al金属。ITO和金属电极间施加正偏压,在不同电流下测试器件的特性,测试结果如表1所示。
表1
NPB指N,N'-二苯基-N,N'-(1-萘基)-1,1'-联苯-4,4'-二胺,TCTA指4,4',4”-三(咔唑-9-基)三苯胺,TPBI指1,3,5-三(1-苯基-1-H-苯并[d]咪唑-2-基)苯(1,3,5-tris(1-phenyl-1H-benzo[d]imidazol-2-yl)benzene)。结构如下:
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
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