CN116375708B - Organic electroluminescent material based on indolospiroacridine and application of organic electroluminescent material in OLED - Google Patents
Organic electroluminescent material based on indolospiroacridine and application of organic electroluminescent material in OLED Download PDFInfo
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- CN116375708B CN116375708B CN202310387116.4A CN202310387116A CN116375708B CN 116375708 B CN116375708 B CN 116375708B CN 202310387116 A CN202310387116 A CN 202310387116A CN 116375708 B CN116375708 B CN 116375708B
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- 239000000463 material Substances 0.000 title claims abstract description 78
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- CINYXYWQPZSTOT-UHFFFAOYSA-N 3-[3-[3,5-bis(3-pyridin-3-ylphenyl)phenyl]phenyl]pyridine Chemical compound C1=CN=CC(C=2C=C(C=CC=2)C=2C=C(C=C(C=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)=C1 CINYXYWQPZSTOT-UHFFFAOYSA-N 0.000 claims description 10
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 claims description 10
- 101150088517 TCTA gene Proteins 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 23
- 239000000203 mixture Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000007787 solid Substances 0.000 description 16
- 238000004440 column chromatography Methods 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 12
- 238000001704 evaporation Methods 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 230000008020 evaporation Effects 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- 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 8
- 238000000746 purification Methods 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- 239000012044 organic layer Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 239000012043 crude product Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000005489 Bromoxynil Substances 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 3
- 238000005401 electroluminescence Methods 0.000 description 3
- 238000001194 electroluminescence spectrum Methods 0.000 description 3
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 3
- 235000011056 potassium acetate Nutrition 0.000 description 3
- 238000006862 quantum yield reaction Methods 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- PPTXVXKCQZKFBN-UHFFFAOYSA-N (S)-(-)-1,1'-Bi-2-naphthol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 PPTXVXKCQZKFBN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- ABRVLXLNVJHDRQ-UHFFFAOYSA-N [2-pyridin-3-yl-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound FC(C1=CC(=CC(=N1)C=1C=NC=CC=1)CN)(F)F ABRVLXLNVJHDRQ-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000009289 huang-lien-chieh-tu-tang Substances 0.000 description 2
- 238000009396 hybridization Methods 0.000 description 2
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- 239000012046 mixed solvent Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 2
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 1
- HKKSDHKJUSSWAI-UHFFFAOYSA-N 1,3-dibromo-2,5-dichlorobenzene Chemical compound ClC1=CC(Br)=C(Cl)C(Br)=C1 HKKSDHKJUSSWAI-UHFFFAOYSA-N 0.000 description 1
- ITPYJIMXMPQSBK-UHFFFAOYSA-N 4-bromo-2,3-difluorobenzonitrile Chemical compound FC1=C(F)C(C#N)=CC=C1Br ITPYJIMXMPQSBK-UHFFFAOYSA-N 0.000 description 1
- KEWDVYIULXXMPP-UHFFFAOYSA-N 9-(2-bromophenyl)carbazole Chemical compound BrC1=CC=CC=C1N1C2=CC=CC=C2C2=CC=CC=C21 KEWDVYIULXXMPP-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ZEEBGORNQSEQBE-UHFFFAOYSA-N [2-(3-phenylphenoxy)-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound C1(=CC(=CC=C1)OC1=NC(=CC(=C1)CN)C(F)(F)F)C1=CC=CC=C1 ZEEBGORNQSEQBE-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/10—Spiro-condensed systems
-
- 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 System
- C07F5/02—Boron compounds
- C07F5/027—Organoboranes and organoborohydrides
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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
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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
- H10K85/60—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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- 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
- H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
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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
- H10K85/658—Organoboranes
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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
- C09K2211/1018—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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
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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
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms
Abstract
The invention discloses an organic electroluminescent material based on indolospiroacridine and application thereof in OLED (organic light emitting diode), and relates to the technical field of organic electroluminescent materials. The invention uses the compound taking indolospiroacridine as the core as the organic electroluminescent material, and the material has both the hRISC and NUV emission characteristics. The organic electroluminescent material has the advantages of simple synthesis method, easily available raw materials, higher yield, stable structure of the obtained material and simple storage. The OLEDs device made of the organic electroluminescent material has higher electroluminescent performance.
Description
Technical Field
The invention belongs to the technical field of organic electroluminescent materials, and particularly relates to an organic electroluminescent material based on indolospiroacridine and application thereof in OLED.
Background
The Organic electroluminescent device is also called Organic Light-Emitting Diodes (OLEDs), which are devices based on Organic luminescent materials and convert electric energy into Light energy, wherein carriers are injected from two electrodes and are composited in a luminescent layer to cause luminescence under the driving of an electric field. The utilization rate of excitons of the OLEDs prepared by using the traditional fluorescent materials can only reach 25%, and the rest 75% of triplet excitons can return to a ground state in a non-radiative decay mode and do not emit light, so that the device efficiency is low; OLEDs based on phosphorescent materials can achieve 100% exciton utilization, but their disadvantages of noble metals, poor stability, high manufacturing cost, etc. limit their practical application in electroluminescent devices. OLEDs based on pure organic thermally activated delayed fluorescence (Thermally Activated Delayed Fluorescent, TADF) materials can fully utilize singlet and triplet excitons generated by electric excitation, realize 100% exciton utilization rate and high device efficiency, but are difficult to realize high exciton utilization rate and high fluorescence radiation efficiency at the same time, the efficiency roll-off is serious, the blue light material efficiency and stability are difficult to break through, complex doping technology is often used, the preparation cost is increased, and the problem of phase separation can occur to reduce the service life of the device.
Hybridization of Charge-Transfer (CT) and Local (LE) states to form a new local-Charge-Transfer hybrid Excited state (Hybridized Local and Charge-Transfer, HLCT) is a new molecular design solution to solve the TADF mechanism problem, which is advantageous for achieving a theoretical 100% exciton utilization (thermal exciton mechanism) from the high-level triplet-to-triplet-state cross-over (RISC formhighertriplet energy levels, hrsc) of the molecule to the singlet state. Meanwhile, the rapid high-energy-level intersystem crossing process can effectively avoid triplet state-triplet state annihilation caused by triplet state exciton accumulation, so that the OLED based on a thermal exciton mechanism often has excellent device stability. In addition, the acceptor strength of the thermoexciton mechanism is moderate, a blue light material with higher color purity is easy to obtain, and the OLED is usually an undoped device, and the preparation process is simple and the cost is low. At present, the material type of the thermal exciton mechanism is single, and development is needed.
Therefore, how to provide an organic electroluminescent material with high solid state light emitting efficiency and high utilization rate of electric excitation excitons is a technical problem to be solved by those skilled in the art.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an organic electroluminescent material based on indolospiracridine, which has high-energy-level triplet-state intersystem crossing (hRISC) and Near Ultraviolet (NUV) emission characteristics,
another object of the present invention is to provide the use of the above-mentioned indolospiracridine-based organic electroluminescent material in the field of organic electroluminescence.
The aim of the invention is achieved by the following scheme:
an organic electroluminescent material based on indolospiroacridine is one of the following compounds:
the compound of the invention takes indolospiroacridine as a core, and weak electron-withdrawing groups are respectively connected to the sites of the No. 3, the No. 6 and the No. 10 sites, so that a series of molecules with the emission spectrum in the deep blue to near ultraviolet band are obtained. Because the indoloaccridine group and the spirofluorene group are connected through sp3 hybridized carbon atoms or silicon atoms, the two parts almost show mutually orthogonal states, the molecular structure is distorted, the molecular distance is large in an aggregation state, the intermolecular interaction is effectively weakened, the exciton annihilation process caused by Dexter energy transfer is slowed down, and strong luminescence is realized in the aggregation state.
In addition, the weak electron donating (D) and the weak electron withdrawing (A) are connected through three different benzene ring loci, so that a certain overlap exists between the highest occupied orbit (HOMO) and the lowest unoccupied orbit (LUMO), molecules with the characteristics of a local-charge Transfer hybridization excitation state (Hybridized Local and Charge-Transfer, HLCT) are formed, the structure is favorable for obtaining higher luminous efficiency, meanwhile, an energy level arrangement with a large energy level difference between a high-energy triplet state and a T1 energy level difference and a small energy level difference between the high-energy triplet state and the singlet state is formed, the efficient utilization of triplet state excitons is realized through the cross-over between the high-energy triplet state opposite systems, the spin statistical limit of the traditional fluorescent material is broken through, and meanwhile, the reverse intersystem leap can be completed rapidly without generating triplet state-triplet state annihilation caused by serious exciton accumulation due to the short service life of the high-energy triplet state excitons, so that the efficiency rolling-down degree of the device is improved.
Therefore, the organic electroluminescent material has the characteristics of high-efficiency solid-state luminescence, high utilization rate of electric excitation excitons, bipolar property and deep blue to near ultraviolet emission. The undoped organic electroluminescent device with high efficiency and low roll-off efficiency can be prepared based on the material, has wide application prospect in the field of organic electroluminescence, and is expected to be widely applied in the fields of flat panel display, solid state lighting and the like.
The invention utilizes the compound as an electroluminescent material to prepare the OLEDs, and the prepared OLEDs comprise undoped OLEDs and doped OLEDs, wherein the undoped OLEDs have the following structure:
ITO/HATCN/TAPC/TcTa/mCP/organic electroluminescent material/PPF/TmPyPB/LiF/Al.
The structure of the doped OLEDs device is as follows:
ITO/HATCN/TAPC/TcTa/mCP/20wt% organic electroluminescent material PPF/TmPyPB/LiF/Al.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention uses the compound taking indolospiroacridine as a core as an organic electroluminescent material, and the material has both the hRISC and NUV emission characteristics.
(2) The organic electroluminescent material has the advantages of simple synthesis method, easily available raw materials, higher yield, stable structure of the obtained material and simple storage.
(3) The OLEDs device prepared by the organic electroluminescent material has higher electroluminescent performance.
Drawings
FIG. 1 is an electroluminescence spectrum of undoped and doped OLEDs prepared using the organic electroluminescent material synthesized in example 1;
FIG. 2 is a graph of L-V-J curves for undoped and doped OLEDs prepared using the organic electroluminescent material synthesized in example 1;
FIG. 3 is a graph showing the efficiency of undoped and doped OLEDs devices prepared using the organic electroluminescent material synthesized in example 1 as a function of luminance;
FIG. 4 is an electroluminescence spectrum of undoped and doped OLEDs prepared using the organic electroluminescent material synthesized in example 2;
fig. 5 is an L-V-J graph of undoped and doped OLEDs devices prepared using the organic electroluminescent material synthesized in example 2.
FIG. 6 is a graph showing the efficiency of undoped and doped OLEDs devices prepared using the organic electroluminescent material synthesized in example 2 as a function of luminance;
FIG. 7 is an electroluminescence spectrum of undoped and doped OLEDs prepared using the organic electroluminescent material synthesized in example 3;
FIG. 8 is a graph of L-V-J curves for undoped and doped OLEDs prepared using the organic electroluminescent material synthesized in example 3;
fig. 9 is a graph showing the efficiency of undoped and doped OLEDs device prepared using the organic electroluminescent material synthesized in example 3 as a function of luminance.
Detailed Description
The invention will be further illustrated with reference to specific examples.
Example 1:
a synthetic method of an organic electroluminescent material (IDSPAC-PhCN-1) based on indolospiroacridine comprises the following steps:
the synthetic route is as follows:
the specific synthesis method is as follows: 9- (2-bromophenyl) -9H-carbazole (6.44 g,20 mmol) and 40mL of tetrahydrofuran were added to a 250mL round bottom flask under nitrogen, placed in a cold trap with stirring and cooled to-78℃and then n-butyllithium (1.6M/L, 18.75mL,30 mmol) was added dropwise via syringe and the resulting mixture was stirred at-78℃for 1 hour, after which the reaction flask was removed and allowed to warm to about 0℃with stirring at room temperature. When the reaction temperature was controlled at about 0 ℃,40mL of a solution of 9-fluorenone (4.14 g,23 mmol) in tetrahydrofuran was added dropwise to the round-bottomed flask, and the mixture was allowed to react at room temperature overnight. To the mixture was added 10mL of water for quenching. After removing most of tetrahydrofuran by evaporation under reduced pressure, the resultant was extracted with methylene chloride (3X 30 mL), and the organic layer was separated, dried over anhydrous sodium sulfate, filtered, and the filtrate was evaporated under reduced pressure to give 8.80g of a pale yellow solid which was used in the next reaction without purification.
The crude product obtained in the previous step was dissolved in 50mL of chloroform and stirred and heated under reflux, and methanesulfonic acid (3.84 g,40 mmol) was then added dropwise to the mixture. After refluxing for 2 hours, the reaction was cooled to room temperature and sodium bicarbonate was added until no gas evolved. After washing with saturated brine (3×50 mL) and evaporation under reduced pressure, IDSPAC was purified by column chromatography to give 42.5% (3.45 g) as a white solid. The detection result of the intermediate IDSPACs is as follows:
1 H NMR(500MHz,CDCl 3 )δ8.30–8.28(d,J＝8.4Hz,1H),8.24–8.22(m,1H),8.20–8.18(d,J＝7.6Hz,1H),7.88–7.83(m,3H),7.65–7.61(m,1H),7.42–7.32(m,4H),7.19–7.13(m,4H),7.08–7.05(m,1H),6.86–6.82(m,1H),6.62–6.60(m,1H),6.52–6.51(m,1H). 13 C NMR(101MHz,CD 2 Cl 2 )δ155.38,139.57,138.54,137.11,136.78,129.32,129.05,128.34,127.97,127.93,126.71,126.25,125.43,124.56,123.25,122.92,122.61,122.51,121.17,121.07,120.17,118.06,114.52,113.73,56.85.
IDSPAC (2.44 g,6 mmol) was added to a round bottom flask (250 mL) containing a solution of tetrahydrofuran (80 mL), stirred in ice water, and then N-bromosuccinimide (NBS) (1.06 g,9 mmol) was dissolved in tetrahydrofuran (40 mL) and added dropwise to the round bottom flask and reacted overnight. After the completion of the reaction, 20mL of water was added to the mixture, most of tetrahydrofuran was removed by evaporation under reduced pressure, the resultant was extracted with methylene chloride (3×30 mL), an organic layer was separated, dried over anhydrous sodium sulfate, filtered, and the filtrate was evaporated under reduced pressure to give a white solid (2.74 g) as compound 1-1, which was used directly for the next reaction without further purification.
A mixture of compound 1-1 (2.74 g), pinacol diboronate (1.90 g,7.5 mmol), 1' -bis (diphenylphosphine) ferrocene palladium (II) dichloride (0.19 g,0.25 mmol) and potassium acetate (0.98 g,10 mmol) was charged to a round bottom flask (250 mL). Three times the gas was evacuated and the system was placed under nitrogen, dry 1, 4-dioxane (80 mL) was poured into the flask and the reaction mixture was heated to reflux for 10h. After cooling to room temperature, the mixture was poured into water and extracted three times with dichloromethane (3×50 mL). The combined organic layers were washed successively with brine and water, and then dried over anhydrous sodium sulfate. After filtration, the filtrate was evaporated under reduced pressure and purified by column chromatography to give 1-2 as a white solid in 20.5% (0.65 g). The detection results of the intermediate 1-2 are as follows:
1 H NMR(500MHz,CDCl 3 )δ8.41(s,1H),8.28–8.27(d,J＝8.4Hz,1H),8.24–8.20(m,2H),7.85–7.83(d,J＝7.6Hz,2H),7.64–7.61(m,1H),7.43–7.37(m,3H),7.32–7.29(m,1H),7.18–7.12(m,4H),6.98(s,1H),6.83–6.80(m,1H),6.55–6.53(m,1H),1.26(s,12H). 13 C NMR(101MHz,CD 2 Cl 2 )δ155.88,140.02,139.29,139.07,137.21,130.23,129.41,129.12,128.82,128.39,128.35,127.20,126.68,125.91,125.88,124.02,123.86,122.74,121.82,121.74,120.72,115.04,114.15,84.11,57.12,25.02.
a mixture of 4-bromoxynil (0.26 g,1.4 mmol), compound 1-2 (0.65 g,1.2 mmol), potassium carbonate (0.5 g,3.6 mmol) and tetrakis (triphenylphosphine) palladium (0.07 g,0.06 mmol) was charged to a round-bottomed flask (100 mL). Three times the system was purged under nitrogen and a mixed liquid of toluene, ethanol and water (8:1:1 v/v,30 mL) was injected into the flask with a syringe. The reaction mixture was heated to 100 ℃ and stirred for 10 hours. After evaporation of the solvent under reduced pressure, purification by column chromatography gave IDSPAC-PhCN-1 as a white solid in 96.2% (0.58 g).
The detection result of the organic electroluminescent material IDSPAC-PhCN-1 of the invention is as follows:
1 H NMR(400MHz,CD 2 Cl 2 )δ8.35–8.33(d,J＝8.3Hz,1H),8.29–8.26(d,J＝8.4Hz,2H),8.16(d,J＝1.6Hz,1H),7.90–7.88(d,J＝7.6Hz,2H),7.72–7.68(m,1H),7.61–7.59(d,J＝8.3Hz,2H),7.52–7.37(m,6H),7.22–7.15(m,4H),6.90–6.86(m,1H),6.73(d,J＝1.6Hz,1H),6.61–6.59(d,9.6H). 13 C NMR(101MHz,CD 2 Cl 2 )δ156.39,147.24,140.95,140.42,138.37,138.13,135.33,133.73,130.70,130.38,129.75,129.43,129.41,128.58,127.37,126.72,124.94,124.60,123.48,122.76,122.66,121.64,120.26,118.46,115.98,115.29,111.43,58.18.HRMS(C 38 H 22 N 2 ):m/z 507.1852[M+H + ,calcd 507.1856]。
example 2
An organic electroluminescent material (IDSPAC-PhCN-2) based on indolospiroacridine has the following structural formula:
the synthetic route is as follows:
wherein the synthesis of idpac is the same as in example 1.
IDSPAC (2.44 g,6 mmol) was added to a round bottom flask (250 mL) containing a solution of tetrahydrofuran (80 mL), stirred in ice water, and then N-bromosuccinimide (NBS) (1.06 g,9 mmol) was dissolved in tetrahydrofuran (40 mL) and added dropwise to the round bottom flask and reacted overnight. After the completion of the reaction, 20mL of water was added to the mixture, most of tetrahydrofuran was removed by evaporation under reduced pressure, the resultant was extracted with methylene chloride (3×30 mL), an organic layer was separated, dried over anhydrous sodium sulfate, filtered, and the filtrate was evaporated under reduced pressure to give a white solid (2.74 g) as compound 2-1, which was used directly for the next reaction without further purification.
A mixture of compound 2-1 (2.74 g), pinacol diboronate (1.90 g,7.5 mmol), 1' -bis (diphenylphosphine) ferrocene palladium (II) dichloride (0.19 g,0.25 mmol) and potassium acetate (0.98 g,10 mmol) was charged to a round bottom flask (250 mL). Three times the gas was evacuated and the system was placed under nitrogen, dry 1, 4-dioxane (80 mL) was poured into the flask and the reaction mixture was heated to reflux for 10h. After cooling to room temperature, the mixture was poured into water and extracted three times with dichloromethane (3×50 mL). The combined organic layers were washed successively with brine and water, and then dried over anhydrous sodium sulfate. Filtering, evaporating the filtrate under reduced pressure, purifying by column chromatography to obtain white solid 2-2, and producingThe yield was 65.0% (2.07 g). 1 H NMR(500MHz,CDCl 3 )δ8.30–8.29(d,J＝8.4Hz,1H),8.22–8.21(d,J＝8.2Hz,1H),8.18–8.16(d,J＝7.6Hz,1H),7.85–7.79(m,4H),7.66–7.62(m,1H),7.43–7.36(m,3H),7.18–7.12(m,4H),7.05–7.02(m,2H),6.44–6.43(d,J＝6.9Hz,1H),1.21(s,12H).
A mixture of 4-bromoxynil (0.84 g,4.6 mmol), compound 2-2 (2.03 g,3.81 mmol), potassium carbonate (1.6 g,11.45 mmol) and tetrakis (triphenylphosphine) palladium (0.23 g,0.19 mmol) was charged to a round-bottomed flask (250 mL). Three times the system was purged under nitrogen and a mixed liquid of toluene, ethanol and water (8:1:1 v/v,120 mL) was injected into the flask with a syringe. The reaction mixture was heated to 100 ℃ and stirred for 10 hours. After evaporation of the solvent under reduced pressure, purification by column chromatography gave IDSPAC-PhCN-2 as a white solid in 83.4% (1.61 g). 1 HNMR(400MHz,CD 2 Cl 2 )δ8.47(d,J＝2.0Hz,1H),8.41–8.39(d,J＝8.8Hz,1H),8.28–8.26(d,J＝8.3Hz,1H),7.98–7.88(m,6H),7.83–7.81(d,J＝8.4Hz,2H),7.44–7.38(m,3H),7.22–7.18(m,2H),7.14–7.10(m,3H),6.91–6.87(m,1H),6.62–6.60(m,1H),6.53–6.51(m,1H). 13 C NMR(126MHz,CD 2 Cl 2 )δ155.75,146.04,140.02,138.94,137.67,137.21,133.16,132.43,129.91,129.65,128.80,128.49,128.43,128.07,127.42,126.26,125.82,125.26,124.06,123.94,123.31,122.91,120.66,120.17,119.46,118.65,115.10,114.56,110.83,57.18.HRMS(C 38 H 22 N 2 ):m/z 507.1869[M+H + ,calcd 507.1856].
Example 3
An organic electroluminescent material (IDSPAC-PhCN-3) based on indolospiroacridine has the following structure:
the synthetic route is as follows:
wherein the synthesis of idpac is the same as in example 1.
IDSPAC (2.44 g,6 mmol) was added to a round bottom flask (250 mL) containing a solution of tetrahydrofuran (80 mL), stirred in ice water, and then N-bromosuccinimide (NBS) (1.06 g,9 mmol) was dissolved in tetrahydrofuran (40 mL) and added dropwise to the round bottom flask and reacted overnight. After the completion of the reaction, 20mL of water was added to the mixture, most of tetrahydrofuran was removed by evaporation under reduced pressure, the resultant was extracted with methylene chloride (3×30 mL), an organic layer was separated, dried over anhydrous sodium sulfate, filtered, and the filtrate was evaporated under reduced pressure to give a white solid (2.74 g) as compound 3-1, which was used directly for the next reaction without further purification.
A mixture of compound 3-1 (2.74 g), pinacol diboronate (1.90 g,7.5 mmol), 1' -bis (diphenylphosphine) ferrocene palladium (II) dichloride (0.19 g,0.25 mmol) and potassium acetate (0.98 g,10 mmol) was charged to a round bottom flask (250 mL). Three times the gas was evacuated and the system was placed under nitrogen, dry 1, 4-dioxane (80 mL) was poured into the flask and the reaction mixture was heated to reflux for 10h. After cooling to room temperature, the mixture was poured into water and extracted three times with dichloromethane (3×50 mL). The combined organic layers were washed successively with brine and water, and then dried over anhydrous sodium sulfate. After filtration, the filtrate was evaporated under reduced pressure and purified by column chromatography to give 3-2 as a white solid in 7.2% (0.23 g). 1 HNMR(400MHz,CDCl 3 )δ8.66(s,1H),8.27–8.23(m,2H),8.08–8.06(d,J＝8.4Hz,1H),7.91–7.89(d,J＝7.6Hz,1H),7.84–7.82(d,J＝7.6Hz,2H),7.39–7.32(m,3H),7.19–7.12(m,4H),7.09–7.05(m,1H),6.87–6.83(m,1H),6.62–6.60(d,J＝7.8Hz,1H),6.52–6.50(d,J＝7.6Hz,2H),1.44(s,12H). 13 C NMR(101MHz,CD2Cl2)δ155.85,140.83,139.99,137.34,137.18,133.52,129.89,129.57,128.77,128.45,128.41,128.35,126.18,125.85,124.93,123.92,123.42,123.22,123.16,120.59,118.62,115.27,113.39,84.27,57.18,25.19.
A mixture of 4-bromoxynil (0.088 g,0.48 mmol), compound 3-2 (0.21 g,0.4 mmol), potassium carbonate (0.2 g,1.44 mmol) and tetrakis (triphenylphosphine) palladium (0.028 g,0.06 mmol) was charged to a round-bottomed flask (100 mL). Drawing machineThe system was purged three times under nitrogen and a mixed liquid of toluene, ethanol and water (8:1:1 v/v,20 mL) was injected into the flask with a syringe. The reaction mixture was heated to 100 ℃ and stirred for 10 hours. After evaporation of the solvent under reduced pressure, purification by column chromatography gave IDSPAC-PhCN-3 as a white solid in 98.4% (0.20 g). 1 H NMR(400MHz,CD 2 Cl 2 )δ8.36–8.31(m,2H),8.23–8.21(d,J＝7.6Hz,1H),7.92–7.88(m,3H),7.69–7.62(m,2H),7.57–7.55(d,J＝8.3Hz,2H),7.46–7.35(m,5H),7.22–7.15(m,4H),7.12–7.08(m,1H),6.85(d,J＝2.4Hz,1H),6.51–6.49(d,J＝7.6Hz,1H). 13 C NMR(101MHz,CD 2 Cl 2 )δ155.46,144.60,140.00,138.88,137.91,137.07,134.10,132.88,130.69,128.84,128.55,128.05,127.28,127.19,126.92,125.80,124.97,123.43,123.33,123.23,121.91,121.72,120.76,119.23,118.64,115.54,114.23,110.83,57.36.HRMS(C 38 H 22 N 2 ):m/z 507.1865[M+H + ,calcd 507.1856].
Example 4
An organic electroluminescent material (IDSPAC-BPh-2) based on indolospiroacridine has the following structure:
the synthetic route is as follows:
1, 3-dibromo-2, 5-dichlorobenzene, phenylboric acid, tetraphenylphosphine palladium and sodium carbonate are added into a reaction bottle, nitrogen is replaced by vacuum pumping for three times, and then a mixed solvent of toluene/ethanol/water (1:0.5:0.5) is added into the reaction bottle, and reflux is carried out for 24 hours at 100 ℃. After the reaction, water was added and extraction was performed with ethyl acetate, the organic phases were combined and the solvent was removed under vacuum to give a crude product. The product 2.5-dichloro-1.3-terphenyl was then purified by column chromatography.
2.5-dichloro-1.3-terphenyl was added to a two-necked flask, nitrogen was replaced three times by vacuum, then super-dry meta-xylene was added, the system was cooled to-40 ℃, then 1 equivalent of n-butyllithium was added, stirring was performed at room temperature for 2 hours, then 2 equivalents of boron tribromide was added at-40 ℃, stirring was performed at room temperature for 2 hours, then diisopropylethylamine was added at 0 ℃, and then reaction was performed at 100 ℃ for 10 hours. After the reaction, distilled water is added for quenching, then dichloromethane extraction is carried out, organic phases are combined, and the solvent is removed under vacuum to obtain a crude product. The product was then purified by column chromatography.
Wherein, the synthesis of the compound 2-2 was the same as that of example 2.
1.3-dibromo-2.5-dichlorobenzene (4.0 g,13.12 mmol), phenylboronic acid (4.0 g,32.8 mmol), tetraphenylphosphine palladium (1.52 g,1.312 mmol), sodium carbonate (7.2 g,65.6 mmol) were charged into a 500mL reaction flask, nitrogen was replaced three times by vacuum, and then a mixed solvent of toluene/ethanol/water (2:1:1 v/v,120 mL) was added into the reaction flask, and refluxed at 100℃for 24 hours. After the reaction, water was added and extraction was performed with ethyl acetate, the organic phases were combined and the solvent was removed under vacuum to give a crude product. The product 2.5-dichloro-1.3-terphenyl (4-1) was then purified by column chromatography. The yield was 65% (2.56 g).
Compound 4-1 (2.0 g,6.72 mmol) was added to a 250mL two-necked flask, nitrogen was replaced three times with vacuum, then ultra-dry meta-xylene (120 mL) was added, the system was cooled to-40 ℃, then 1 equivalent of n-butyllithium (2.4M, 2.8mL,6.72 mmol) was added, stirred at room temperature for 2h, then 2 equivalents of boron tribromide (1M, 13.6mL,13.44 mmol) was added at-40 ℃, stirred at room temperature for 2h, then diisopropylethylamine (1.76 g,13.44 mmol) was added at 0 ℃, and then reacted at 100℃for 10h. After the reaction, distilled water is added for quenching, then dichloromethane extraction is carried out, organic phases are combined, and the solvent is removed under vacuum to obtain a crude product. The product 4-2 was then purified by column chromatography in 7% (0.12 g) yield.
A mixture of compound 4-2 (0.12 g,0.44 mmol), compound 2-2 (0.23 g,0.44 mmol), cesium carbonate (0.43 g,1.32 mmol) and tris (dibenzylideneacetone) dipalladium (0.021 g,0.02 mmol) was charged to a round bottom flask (100 mL). The system was purged three times under nitrogen and a mixed liquid of 1, 4-dioxane (20 mL) was injected into the flask with a syringe. The reaction mixture was heated to reflux and stirred for 10 hours. The solvent was evaporated under reduced pressure and purified by column chromatography to give IDSPAC-BPh-2 as a white solid.
Example 5
An organic electroluminescent material ((S) -/(R) -BNPCN-p-IDSPAC) based on indolospirudine, which has the following structure:
the synthetic route is as follows:
a mixture of 4-bromo-2, 3-difluorobenzonitrile (1.31 g,6.00 mmol), (S) -/(R) -1,1' -bi-2-naphthol (1.72 g,6.0 mmol) and potassium carbonate (1.66 g,12.0 mmol) was added to 30mL dry N, N-dimethylformamide (100 mL). The reaction mixture was then stirred at 100 ℃ for 20 hours. After cooling the mixture to room temperature, the solvent was evaporated under reduced pressure and the residue was purified by column chromatography on silica gel (dichloromethane: petroleum ether, 1:2 v/v) to give (S) -/(R) -5-1 as a white solid in 57% yield (1.58 g).
The synthesis of compound 2-2 was the same as in example 2.
A mixture of compound (S) -/(R) -5-1 (0.85 g,1.8 mmol), compound 2-2 (0.80 g,1.5 mmol), potassium carbonate (0.75 g,5.4 mmol) and tetrakis (triphenylphosphine) palladium (0.11 g,0.09 mmol) was charged to a round-bottomed flask (100 mL). Three times the system was purged under nitrogen and a mixed liquid of toluene, ethanol and water (8:1:1 v/v,40 mL) was injected into the flask with a syringe. The reaction mixture was heated to 100 ℃ and stirred for 10 hours. After evaporation of the solvent under reduced pressure, purification by column chromatography gave (S) -/(R) -BNPCN-p-IDSPAC as a white solid in 87.2% (1.04 g).
Example 6
Undoped OLEDs and doped OLEDs were prepared using the organic electroluminescent material (idpac-PhCN-1, thin film fluorescence quantum yield 68%) synthesized in example 1, and the results of testing and characterizing the OLEDs are shown in fig. 1 to 3.
The device structure is as follows: ITO/HATCN/TAPC/TcTa/mCP/organic electroluminescent material/PPF/TmPyPB/LiF/Al. (undoped structure);
ITO/HATCN/TAPC/TcTa/mCP/20wt% organic electroluminescent material PPF/PPF/TmPyPB/LiF/Al. (doping structure);
as can be seen from fig. 1, the maximum emission peaks of the undoped and doped devices based on idpac-PhCN-1 are 402nm,396nm, respectively, belonging to the near ultraviolet light emitting region.
As can be seen from FIG. 2, the maximum brightness of the undoped and doped devices based on IDSPACE-PhCN-1 is high and the starting voltage is low, respectively 2018cd/m 2 3.1V and 553cd/m 2 ，3.2V。
As can be seen from FIG. 3, the maximum current efficiency and the power efficiency of the undoped device and the doped device based on IDSPAC-PhCN-1 are respectively higher, namely 2.27cd/A and 0.77lmW -1 And 0.69cd/A,0.65lm W -1 Undoped devices based on IDSPAC-PhCN-1 and doped with their maximum external quantum efficiencies of 6.21% and 5.77%, respectively, when the luminance was 1000cd/m 2 When undoped device external quantum efficiency was maintained at 3.78%.
Example 7
Undoped OLEDs and doped OLEDs were prepared using the organic electroluminescent material (idpac-PhCN-2, thin film fluorescence quantum yield 78%) synthesized in example 2, and the results of testing and characterizing the OLEDs are shown in fig. 4 to 6.
The device structure is as follows: ITO/HATCN/TAPC/TcTa/mCP/organic electroluminescent material/PPF/TmPyPB/LiF/Al. (undoped structure);
ITO/HATCN/TAPC/TcTa/mCP/20wt% organic electroluminescent material PPF/PPF/TmPyPB/LiF/Al. (doping structure);
as can be seen from FIG. 4, the maximum emission peaks of the undoped and doped devices based on IDSPAC-PhCN-2 are respectively 406nm and 402nm, and belong to the near ultraviolet light emitting region.
As can be seen from fig. 5, the baseThe maximum brightness of undoped and doped devices in IDSPAC-PhCN-2 was high and the threshold voltage was low, 7176cd/m respectively 2 2.9V and 1103cd/m 2 ，3.1V。
As can be seen from FIG. 5, the maximum current efficiency and the power efficiency of the undoped and doped IDSPACE-PhCN-2-based devices were 1.68cd/A,1.76lmW, respectively -1 And 1.12cd/A,1.10lmW -1 Undoped and doped devices based on idpac-PhCN-2 have maximum external quantum efficiencies of 7.90% and 6.61%, respectively, when the luminance is 1000cd/m 2 When the external quantum efficiency was maintained at 6.64% and 2.12%, respectively.
Example 8
Undoped OLEDs and doped OLEDs were prepared using the organic electroluminescent material (idpac-PhCN-3, thin film fluorescence quantum yield 90%) synthesized in example 3, and the results of testing and characterizing the OLEDs are shown in fig. 7 to 9.
The device structure is as follows: ITO/HATCN/TAPC/TcTa/mCP/organic electroluminescent material/PPF/TmPyPB/LiF/Al. (undoped structure);
ITO/HATCN/TAPC/TcTa/mCP/20wt% organic electroluminescent material PPF/PPF/TmPyPB/LiF/Al. (doping structure);
as can be seen from fig. 7, the maximum emission peaks of the undoped and doped devices based on idpac-PhCN-3 are 414nm, respectively, belonging to the near ultraviolet light emitting region.
As can be seen from FIG. 8, the maximum brightness of the IDSPAC-PhCN-3 based undoped and doped devices is high and the threshold voltage is low, respectively 5040cd/m 2 3.1V and 1656cd/m 2 ，3.1V。
As can be seen from FIG. 9, the maximum current efficiency and the power efficiency of the undoped and doped IDSPACE-PhCN-3-based devices were 1.44cd/A,1.33lmW, respectively -1 And 1.39cd/A,1.36lmW -1 The method comprises the steps of carrying out a first treatment on the surface of the Undoped and doped devices based on IDSPAC-PhCN-3 have maximum external quantum efficiencies of 6.24% and 6.68%, respectively, when the luminance is 1000cd/m 2 When the external quantum efficiency was maintained at 5.18% and 3.24%, respectively.
The data show that the invention takes indolospiroacridine as a core, and respectively connects electron-donating groups at three different active sites, so that the hRISC and NUV characteristics can be organically combined in one molecule, and the doped OLEDs device prepared by taking the materials as a light-emitting layer has higher efficiency and smaller efficiency roll-off degree; the undoped OLEDs prepared based on the material has the advantages of simple structure, lower starting voltage, higher efficiency and smaller efficiency roll-off degree. In a word, the material has a very wide application prospect in the field of organic electroluminescence.
It should be noted that the above-mentioned embodiments are only a few specific embodiments of the present invention, and it is obvious that the present invention is not limited to the above embodiments, but other modifications are possible. All modifications directly or indirectly derived from the disclosure of the present invention will be considered to be within the scope of the present invention.
Claims (9)
1. An organic electroluminescent material based on indolospiroacridine is characterized in that the organic electroluminescent material is one of the following compounds:
2. the organic electroluminescent material based on indolospiracridine according to claim 1, wherein the synthetic route of the organic electroluminescent material IDSPAC-PhCN-1 is as follows:
。
3. the organic electroluminescent material based on indolospiracridine according to claim 1, wherein the synthetic route of the organic electroluminescent material IDSPAC-PhCN-2 is as follows:
。
4. the organic electroluminescent material based on indolospiracridine according to claim 1, wherein the synthetic route of the organic electroluminescent material IDSPAC-PhCN-3 is as follows:
。
5. the organic electroluminescent material based on indolospiroacridine according to claim 1, wherein the synthetic route of the organic electroluminescent material IDSPAC-BPh-2 is as follows:
6. the organic electroluminescent material based on indolospiracridine according to claim 1, characterized in that the synthetic route of the organic electroluminescent material (S) -/(R) -BNPCN-p-idpac is as follows:
7. use of an organic electroluminescent material based on indolospiracridine according to claim 1 in an OLED, characterized in that the compound as luminescent material is used for the preparation of undoped OLEDs and doped OLEDs, respectively, in an undoped or doped manner.
8. The use of claim 7, wherein the undoped OLEDs device is structured as follows:
ITO/HATCN/TAPC/TcTa/mCP/organic electroluminescent material/PPF/TmPyPB/LiF/Al.
9. The use of claim 7, wherein the doped OLEDs device has the structure:
ITO/HATCN/TAPC/TcTa/mCP/20wt% organic electroluminescent material PPF/TmPyPB/LiF/Al.
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| WO2019085759A1 (en) * | 2017-11-03 | 2019-05-09 | 江苏三月光电科技有限公司 | Compound provided with an aza-spirofluorene and aryl ketone core, preparation method thereof, and application of same in oleds |
| CN115819421A (en) * | 2022-12-23 | 2023-03-21 | 华南理工大学 | Deep red light/near infrared organic electroluminescent material, preparation method thereof and application thereof in preparing OLED |
| CN115850290A (en) * | 2022-10-24 | 2023-03-28 | 华南理工大学 | Organic electroluminescent material based on heteroanthrone five-membered ring and application thereof in OLED |
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| WO2019085759A1 (en) * | 2017-11-03 | 2019-05-09 | 江苏三月光电科技有限公司 | Compound provided with an aza-spirofluorene and aryl ketone core, preparation method thereof, and application of same in oleds |
| CN115850290A (en) * | 2022-10-24 | 2023-03-28 | 华南理工大学 | Organic electroluminescent material based on heteroanthrone five-membered ring and application thereof in OLED |
| CN115819421A (en) * | 2022-12-23 | 2023-03-21 | 华南理工大学 | Deep red light/near infrared organic electroluminescent material, preparation method thereof and application thereof in preparing OLED |
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