CN112175016B - Organic electrophosphorescent luminescent material and application thereof - Google Patents
Organic electrophosphorescent luminescent material and application thereof Download PDFInfo
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- CN112175016B CN112175016B CN202011222272.8A CN202011222272A CN112175016B CN 112175016 B CN112175016 B CN 112175016B CN 202011222272 A CN202011222272 A CN 202011222272A CN 112175016 B CN112175016 B CN 112175016B
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- organic electroluminescent
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- 239000000463 material Substances 0.000 title claims abstract description 97
- 150000001875 compounds Chemical class 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 125000001424 substituent group Chemical group 0.000 claims description 20
- 125000004429 atom Chemical group 0.000 claims description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 16
- 229910052731 fluorine Inorganic materials 0.000 claims description 11
- 125000001153 fluoro group Chemical group F* 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- 229910052805 deuterium Inorganic materials 0.000 claims description 10
- 238000006467 substitution reaction Methods 0.000 claims description 9
- 125000005605 benzo group Chemical group 0.000 claims description 8
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 8
- -1 C 1 ~C 5 Alkyl group Chemical group 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 125000004431 deuterium atom Chemical group 0.000 claims 1
- 239000010410 layer Substances 0.000 description 53
- 239000003446 ligand Substances 0.000 description 26
- 229910052757 nitrogen Inorganic materials 0.000 description 25
- 125000000623 heterocyclic group Chemical group 0.000 description 18
- 229910052739 hydrogen Inorganic materials 0.000 description 16
- 239000007787 solid Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000001704 evaporation Methods 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 230000008020 evaporation Effects 0.000 description 12
- 238000010992 reflux Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 9
- 125000005842 heteroatom Chemical group 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000000921 elemental analysis Methods 0.000 description 8
- 230000005525 hole transport Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 7
- 150000001975 deuterium Chemical group 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000012074 organic phase Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 125000003282 alkyl amino group Chemical group 0.000 description 6
- 125000004414 alkyl thio group Chemical group 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229910052741 iridium Inorganic materials 0.000 description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 description 6
- 125000004430 oxygen atom Chemical group O* 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 125000004434 sulfur atom Chemical group 0.000 description 6
- 239000010408 film Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 238000010907 mechanical stirring Methods 0.000 description 5
- 238000000859 sublimation Methods 0.000 description 5
- 230000008022 sublimation Effects 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 150000001555 benzenes Chemical group 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- NZCKTGCKFJDGFD-UHFFFAOYSA-N 2-bromobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Br NZCKTGCKFJDGFD-UHFFFAOYSA-N 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- PWKNBLFSJAVFAB-UHFFFAOYSA-N 1-fluoro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1F PWKNBLFSJAVFAB-UHFFFAOYSA-N 0.000 description 2
- 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 2
- AOPBDRUWRLBSDB-UHFFFAOYSA-N 2-bromoaniline Chemical compound NC1=CC=CC=C1Br AOPBDRUWRLBSDB-UHFFFAOYSA-N 0.000 description 2
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 2
- 125000004070 6 membered heterocyclic group Chemical group 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- YOLNUNVVUJULQZ-UHFFFAOYSA-J iridium;tetrachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Ir] YOLNUNVVUJULQZ-UHFFFAOYSA-J 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- IMJNGEAWYAFBJZ-UHFFFAOYSA-N 1-fluoro-2-nitro-4-propan-2-ylbenzene Chemical compound CC(C)C1=CC=C(F)C([N+]([O-])=O)=C1 IMJNGEAWYAFBJZ-UHFFFAOYSA-N 0.000 description 1
- UVRRJILIXQAAFK-UHFFFAOYSA-N 2-bromo-4-methylaniline Chemical compound CC1=CC=C(N)C(Br)=C1 UVRRJILIXQAAFK-UHFFFAOYSA-N 0.000 description 1
- QYGFJEIQODJAQF-UHFFFAOYSA-N 2-bromo-4-methylbenzoyl chloride Chemical compound CC1=CC=C(C(Cl)=O)C(Br)=C1 QYGFJEIQODJAQF-UHFFFAOYSA-N 0.000 description 1
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- TXRDVLWLDIQNJJ-UHFFFAOYSA-N BrC1=C(C=CC2=C1OC1=C2C=CC=C1)C(=O)Cl Chemical compound BrC1=C(C=CC2=C1OC1=C2C=CC=C1)C(=O)Cl TXRDVLWLDIQNJJ-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- CZKMPDNXOGQMFW-UHFFFAOYSA-N chloro(triethyl)germane Chemical compound CC[Ge](Cl)(CC)CC CZKMPDNXOGQMFW-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XTLNYNMNUCLWEZ-UHFFFAOYSA-N ethanol;propan-2-one Chemical compound CCO.CC(C)=O XTLNYNMNUCLWEZ-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- JVZRCNQLWOELDU-UHFFFAOYSA-N gamma-Phenylpyridine Natural products C1=CC=CC=C1C1=CC=NC=C1 JVZRCNQLWOELDU-UHFFFAOYSA-N 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000002506 high-vacuum sublimation Methods 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001012 protector Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 description 1
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 description 1
- 238000005092 sublimation method Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
Classifications
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- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
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- 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
-
- 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
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
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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
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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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
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
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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
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
- C09K2211/1051—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with sulfur
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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
- C09K2211/18—Metal complexes
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Abstract
The invention relates to the technical field of organic electroluminescent display, and particularly discloses a novel organic electrophosphorescent luminescent material and application thereof in an organic electroluminescent device. The organic electrophosphorescent luminescent material provided by the invention has a structure shown as a general formula (I). The organic electrophosphorescent luminescent material is applied to an organic electroluminescent device, and the prepared electroluminescent device has the superior performances of high purity, high brightness and high efficiency.
Description
Technical Field
The invention relates to the technical field of organic electroluminescent display, and particularly discloses a novel organic electrophosphorescent luminescent material and application thereof in an organic electroluminescent device.
Background
Electroluminescent display devices can be classified into inorganic electroluminescent display devices and organic electroluminescent display devices according to the difference in the material constituting the light emitting layer. Organic electroluminescent display devices have incomparable advantages with inorganic electroluminescent display devices, such as full-color luminescence in the visible spectrum, extremely high brightness, extremely low driving voltage, fast response time, and simple manufacturing processes.
The research of organic electroluminescence starts in the 60 th 19 th century, pope firstElectroluminescence is realized on anthracene single crystal, but the driving voltage is as high as 100V, and the quantum efficiency is low. In 1987, tang and VanSlyke adopted a double-layer thin film structure with 8-hydroxyquinoline aluminum complex (Alq 3) as a light-emitting layer and an electron transport layer and TAPC as a hole transport layer, and ITO electrodes and Mg: ag electrodes were used as an anode and a cathode, respectively, to prepare (A) a high-brightness>1000cd/m 2 ) The driving voltage of the green organic electroluminescent thin-film device with high efficiency (1.5 lm/W) is reduced to below 10V. In 1990, polymer thin film electroluminescent devices made from poly (p-phenylene vinylene) (PPV) by Burroughes et al gave blue-green light output with quantum efficiency of 0.05% and driving voltage of less than 14V. In 1991, braun et al produced green and orange light outputs with quantum efficiencies of 1% with derivatives of PPV, and drive voltages of about 3V. These research advances have immediately attracted considerable attention from scientists of various countries, and research on organic electroluminescence has been widely conducted worldwide and has gradually started to move to the market.
In general, an organic electroluminescent display device has a structure including an anode formed on a substrate, and a hole transport layer, a light emitting layer, an electron transport layer, and a cathode sequentially formed on the anode. The hole transport layer, the light emitting layer, and the electron transport layer are organic thin films composed of organic compounds. The driving principle of the organic electroluminescent display device having the above-described structure is as follows: holes are injected from the anode into the light-emitting layer through the hole transport layer as long as a voltage is applied between the anode and the cathode; at the same time, electrons are injected from the cathode into the light-emitting layer through the electron transport layer; in the light emitting layer region, carriers are rearranged to form excitons, and the excited excitons are turned to the ground state, causing light emission from the light emitting layer molecules.
Light emitting materials are classified into two groups according to the mechanism of light emission, one group being fluorescent materials using singlet excitons, and the other group being phosphorescent materials using triplet excitons. The phosphorescent material has higher luminous efficiency than the fluorescent material because the phosphorescent material can utilize 75% of triplet excitons and 25% of singlet excitons, whereas the fluorescent material utilizes only 25% of singlet excitons. Phosphorescent materials are generally organometallic compounds containing heavy metals, which form a light-emitting layer composed of a host material and a dopant material that emits light by transferring energy from the host material.
At present, organometallic complexes having phosphorescent emission and organic electroluminescent devices are reported, and various organometallic complex phosphorescent materials are also disclosed in the patent. For example, US patent No. 6687266 discloses Ir complexes containing benzimidazole ligands, which have hindered the possibility of commercialization due to the serious problems of low phosphorescence efficiency, poor stability and lifetime. Therefore, it would be of great significance to structurally improve such compounds to develop new phosphorescent light-emitting materials with better performance and promote commercial application.
Disclosure of Invention
The invention aims to develop a novel organic electrophosphorescent luminescent material, which is applied to an organic electroluminescent device, and the prepared electroluminescent device has the excellent performances of high purity, high brightness and high efficiency.
Specifically, in a first aspect, the present invention provides an organic electrophosphorescent material having a structure represented by general formula (i):
wherein:
R 1 ～R 11 independently selected from hydrogen atom, deuterium atom, alkyl group, deuterated alkyl group, cyano group, alkoxy group, alkylamino group, alkylthio group, fluorine atom, trifluoromethyl group, aryl group and heterocyclic aryl group, and/or R 1 ～R 11 Wherein adjacent substituents form a fused ring structure by bridging;
l is a monovalent bidentate anion, wherein the bonding atoms X, Y are each independently selected from the group consisting of oxygen atoms, nitrogen atoms, carbon atoms;
n is 1, 2 or 3.
As a preferred embodiment of the present invention, said L is a monovalent bidentate anionic ligand, preferably said L is phenylpyridyl, substituted phenylpyridyl, acetylacetonate or substituted acetylacetonate.
Further preferably, L is a group of formula L1 or formula L2:
wherein: in the formula L1, R 12 ～R 19 Independently selected from hydrogen atom, deuterium atom, alkyl group, deuterated alkyl group, alkoxy group, alkylamino group, alkylthio group, fluorine atom, trifluoromethyl group, aryl group and heterocyclic aryl group, and/or R 12 ～R 19 Wherein adjacent substituents form a fused ring structure by bridging.
Wherein, in the formula L2, R 20 ～R 26 Independently selected from hydrogen atom, deuterium atom, alkyl group, deuterated alkyl group, alkoxy group, alkylamino group, alkylthio group, fluorine atom, trifluoromethyl group, aryl group and heterocyclic aryl group, and/or R 20 ～R 26 Wherein adjacent substituents form a fused ring structure by bridging.
As a more preferred embodiment of the present invention, L is arbitrarily selected from the following groups:
as a preferred embodiment of the present invention, the phosphorescent light emitting material is a compound represented by formula I or formula II or formula III:
wherein m is 1 or 2.
R in the general formula I 1 ～R 11 As previously defined.
R in formula II or formula III 1 ～R 26 As previously defined.
As a preferred embodiment of the present invention, the above general formula (I)) Or in the general formula I or II or III, where R 1 ～R 11 Each independently selected from hydrogen atom, deuterium atom, and C 1 ～C 5 Alkyl of (C) 1 ～C 5 Deuterated alkyl, cyano, alkoxy containing 1-5C atoms, alkylamino containing 1-5C atoms, alkylthio containing 1-5C atoms, fluorine atom, trifluoromethyl, phenyl, substituted phenyl and heterocyclic aromatic group; or, R 1 ～R 11 Wherein adjacent substituent groups form a fused ring structure through bridging, the fused ring structure is any one of a substituted or unsubstituted five-membered ring, a substituted or unsubstituted six-membered ring, a substituted or unsubstituted five-membered heterocycle and a substituted or unsubstituted six-membered heterocycle, and the substituent group adopted for substitution is C 1 ～C 5 The number of the hetero atoms contained in the five-membered heterocyclic ring or the six-membered heterocyclic ring is at least one, and the hetero atoms are selected from oxygen atoms, sulfur atoms and nitrogen atoms.
In this application, C 1 ～C 5 The alkyl group of (b) may be a straight-chain alkyl group or a branched-chain alkyl group such as methyl, ethyl, n-propane, isopropyl, sec-butyl, n-butyl, isobutyl, tert-butyl, pentyl, neopentyl and the like.
C 1 ～C 5 Is C with part of the hydrogen atoms being replaced by deuterium 1 ～C 5 Alkyl of (2), likewise C 1 ～C 5 The alkyl group of (a) may be a straight-chain alkyl group or an alkyl group having a branched chain. C 1 ～C 5 The deuterated alkyl group in (b) can be, for example, deuterated methyl, deuterated isopropyl, deuterated pentyl, deuterated neopentyl, etc.
Alkoxy containing 1 to 5C atoms is C n H 2n+1 O-, wherein n is 1 to 5. The alkoxy group having 1 to 5 carbon atoms may be a methoxy group, an ethoxy group or the like.
R 1 ～R 11 May also form a fused-ring structure by bridging, and when the fused-ring structure is formed, the fused-ring structure may be any one of a substituted or unsubstituted five-membered ring, a substituted or unsubstituted six-membered ring, a substituted or unsubstituted five-membered heterocyclic ring, and a substituted or unsubstituted six-membered heterocyclic ring. At least one heteroatom is contained in the five-membered heterocyclic ring or the six-membered heterocyclic ring, and the heteroatom is selected from oxygen atom, sulfur atom and nitrogen atom. For example, the fused ring structure may be a benzo ring, a furo ring, a thieno ring, a cyclopenteno ring or the like. The fused ring structure may be further substituted with a substituent, for example, with a benzo group, with an alkyl group, or the like.
As a preferred embodiment of the present invention, in the general formula II, R is as described above 12 ～R 19 Each independently selected from hydrogen atom, deuterium atom, C 1 ～C 5 Alkyl group, fluorine atom, phenyl group, substituted phenyl group, C 1 ～C 5 Deuterated alkyl, cyano, alkoxy containing 1-5C atoms, alkylamino containing 1-5C atoms, alkylthio containing 1-5C atoms, trifluoromethyl and heterocyclic aromatic group; or, R 12 ～R 19 Wherein adjacent substituents form a fused ring structure through bridging, the fused ring structure is any one of a substituted or unsubstituted five-membered ring, a substituted or unsubstituted six-membered ring, a substituted or unsubstituted five-membered heterocyclic ring and a substituted or unsubstituted six-membered heterocyclic ring, and the substituent adopted for substitution is C 1 ～C 5 The alkyl, phenyl, benzo, pyrido, alkyl-substituted pyrido, deuterated alkyl-substituted pyrido, the five-membered heterocycle or six-membered heterocycle contains at least one heteroatom, and the heteroatom is selected from oxygen atom, sulfur atom, and nitrogen atom.
As a preferred embodiment of the present invention, in the formula III, R is as defined in the description 20 ～R 26 Each independently selected from hydrogen atom, deuterium atom, C 1 ～C 5 Alkyl group, fluorine atom, C 1 ～C 5 Deuterated alkyl, alkoxy containing 1-5C atoms, alkylamino containing 1-5C atoms, alkylthio containing 1-5C atoms and trifluoromethyl.
As a further preferred embodiment of the present invention, in the above general formula (I) or general formula I or general formula II or general formula III, wherein R is 1 ～R 11 Each independently selected from hydrogen atom and C 1 ～C 5 Alkyl of (C) 1 ～C 5 Deuterated alkyl, benzeneFluorine atom, alkoxy containing 1-5C atoms, trifluoromethyl; or, R 1 ～R 11 Wherein adjacent substituents form a fused ring structure through bridging, the fused ring structure is any one of a substituted or unsubstituted five-membered ring, a substituted or unsubstituted benzene ring and a substituted or unsubstituted five-membered heterocycle, and the substituent adopted for substitution is C 1 ～C 5 At least one heteroatom of the five-membered heterocyclic ring is selected from oxygen atom and sulfur atom.
More preferably, wherein R 1 ～R 11 Independently selected from hydrogen atom, methyl, deuterated methyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, deuterated isopropyl, phenyl, pentyl, deuterated pentyl, fluorine atom and methoxyl; or, R 1 ～R 11 Wherein adjacent substituents form a fused ring structure through bridging, the fused ring structure is any one of a substituted or unsubstituted benzene ring, a substituted or unsubstituted furan ring, a substituted or unsubstituted thiophene ring and a substituted or unsubstituted cyclopentene ring, and the substituents adopted for substitution are a benzo group and a methyl group.
As a further preferred embodiment of the present invention, in formula II, said R is 12 ～R 19 Each independently selected from hydrogen atom and C 1 ～C 5 Alkyl group, fluorine atom, phenyl group, C 1 ～C 5 Deuterated alkyl of (a); or, R 12 ～R 19 Wherein adjacent substituent groups form a fused ring structure through bridging, the fused ring structure is any one of a substituted or unsubstituted benzene ring and a substituted or unsubstituted five-membered heterocycle, and the substituent group adopted by the substitution is C 1 ～C 5 The heterocyclic ring is an alkyl group, a phenyl group, a benzo group, a pyrido group, an alkyl group substituted pyrido group containing 1 to 5C atoms, or a deuterated alkyl group substituted pyrido group containing 1 to 5C atoms, the five-membered heterocyclic ring contains at least one heteroatom, and the heteroatom is optionally selected from an oxygen atom and a sulfur atom.
More preferably, wherein R 12 ～R 19 Each independently selected from hydrogen atom, methyl, fluorine atom, phenyl and deuteromethylAlkyl, isopropyl, deuterated isopropyl; or, R 12 ～R 19 Wherein adjacent substituents form a fused ring structure through bridging, the fused ring structure is any one of a substituted or unsubstituted benzene ring, a substituted or unsubstituted furan ring and a substituted or unsubstituted six-membered ring, and the substituent adopted for substitution is a deuterated methyl-substituted pyrido group, a methyl-substituted pyrido group or a benzo group.
As a further preferable embodiment of the present invention, in the above general formula III, said R 20 ～R 26 Each independently selected from hydrogen atom, deuterium atom, and C 1 ～C 5 Alkyl group of (1).
More preferably, wherein R 20 ～R 26 Each independently selected from hydrogen atom, methyl group and ethyl group.
As a preferred embodiment of the present invention, the organic electrophosphorescent material is selected from compounds represented by the following structural formula:
in the research, the iridium-containing complex containing benzimidazole structural units as main ligands is found to be shown as the following formula,
the purity of the material is obviously reduced in the sublimation process, which indicates that the material is not suitable for preparing an OLED panel by the evaporation technology at present. Theoretical analysis and experiment prove that the instability of the material comes from N-C bonds formed by N atoms on benzimidazole and groups connected with the N atoms in the ligand, and weaker C-N bonds tend to be broken and decomposed at high temperature to reduce the purity. Through a large number of experiments, we find that two benzene rings are connected through an S atom to form a ring structure, namely a mother nucleus structure shown in the following formula:
the probability of degradation of the molecules is greatly reduced by the entropy effect. Meanwhile, the introduction of a ring structure is found to effectively improve the rigidity of the ligand and weaken the excited state nonradiative transition mechanism, so that the phosphorescence quantum efficiency of the iridium-containing phosphorescent material supported by the ligand is improved.
The invention provides a novel organic electrophosphorescent luminescent material which can be used as a red-green phosphorescent luminescent material. The phosphorescent material provided by the invention can effectively solve the problems of the conventional phosphorescent material in the aspects of color purity, luminous efficiency, service life and the like, and an organic electroluminescent device prepared by using the phosphorescent material provided by the invention has excellent performances of high purity, high brightness and high efficiency.
Specifically, the novel organic electrophosphorescent material provided by the invention is a phosphorescent material supported by a benzimidazole ligand with a cyclic structure, and compared with an iridium-containing compound formed by an acyclic benzimidazole ligand, the iridium-containing complex formed by the cyclic benzimidazole ligand has the following advantages:
(1) According to the complex, two aromatic groups on the benzimidazole ligand form a ring, so that the tendency of high-temperature thermal decomposition of phosphorescent molecules caused by the existence of a weaker C-N bond can be reduced, the thermal stability of the material is improved, the phenomenon of purity reduction in the sublimation or evaporation process is reduced, and the commercialization of the material is possible;
(2) The stability of the material is improved, so that the stability of an OLED device applying the material is improved, namely the service life is prolonged;
(3) The complex increases the rigidity of ligand molecules due to cyclization, weakens the non-radiative transition mechanism of the excited state of phosphorescent molecules, thereby improving the phosphorescent quantum efficiency of the material, showing that the luminous efficiency on a device is improved, and bringing positive effects for reducing the power consumption of an OLED screen body.
The novel iridium-containing material supported by the cyclized benzimidazole structural unit ligand provided by the invention is used as a luminescent layer luminescent material of an organic electroluminescent device, can improve the phosphorescence quantum efficiency and electroluminescent efficiency of the material, and improves the stability of the material and the service life of the device.
In a second aspect, the invention provides the application of the organic electrophosphorescent luminescent material in the preparation of organic electroluminescent devices.
Preferably, the organic electrophosphorescent luminescent material is used as a dye material of a host material in an organic electroluminescent device. The material of the invention is used as a dye doped in an organic electroluminescent device to emit light, and the electroluminescent device prepared by utilizing the phosphorescent material of the invention has the superior performances of high purity, high brightness and high efficiency.
More preferably, the doping concentration of the phosphorescent light-emitting material in the host material is 3 to 12%, more preferably 5 to 10%, and still more preferably 7 to 9%. When the doping concentration of the phosphorescent light-emitting material in the host material is about 8%, the performance of the device is best. The doping concentration is mass percentage concentration.
In a third aspect, the present invention provides an organic electroluminescent device comprising a light-emitting layer comprising the phosphorescent light-emitting material provided by the present invention.
Preferably, the light emitting layer includes a host material and a dye material, and the dye material includes the phosphorescent light emitting material provided by the present invention.
Further preferably, the doping concentration of the phosphorescent light-emitting material in the host material is 3 to 12%, more preferably 5 to 10%, more preferably 7 to 9%, and more preferably 8%.
Specifically, the invention provides an organic electroluminescent device, which comprises a substrate, and an anode layer, a plurality of light-emitting unit layers and a cathode layer which are sequentially formed on the substrate; the light-emitting unit layer comprises a hole injection layer, a hole transport layer, a light-emitting layer and an electron transport layer, wherein the hole injection layer is formed on the anode layer, the hole transport layer is formed on the hole injection layer, the cathode layer is formed on the electron transport layer, and a plurality of light-emitting layers are arranged between the hole transport layer and the electron transport layer. The luminescent material of the luminescent layer is the iridium-containing phosphorescent luminescent material provided by the invention.
In a fourth aspect, the invention further provides a display device comprising the organic electroluminescent device.
In a fifth aspect, the invention further provides a lighting device comprising the organic electroluminescent device.
Detailed Description
The technical solution of the present invention will be described in detail by specific examples. The following examples are intended to illustrate the present invention, but are not intended to limit the scope of the present invention, and other equivalent changes or modifications made without departing from the spirit of the present invention are intended to be included within the scope of the appended claims.
Example 1: synthesis of ligand P1
The synthetic route is as follows:
the specific experimental steps are as follows:
(1) 2-fluoronitrobenzene (14.1g, 0.1mol) and 2-bromoaniline (25.7g, 0.15mol) are added into a 2L three-neck flask with mechanical stirring, stirred and heated to 180 ℃ under the protection of argon, the temperature is kept for reaction for more than 30 hours, and the color gradually turns into red in the reaction process and finally turns into deep red gradually. After the reaction was completed, the organic phase was separated, extracted, dried, column chromatographed, and the solvent was spin-dried to obtain 24.8g of an orange-red solid M1 with a yield of 85%.
(2) To a 1L three-necked flask equipped with a mechanical stirrer, M1 (29.2g, 0.1 mol), sodium sulfide nonahydrate (96g, 0.4 mol), ethanol (200 mL), water (100 mL) and nitrogen were added, and the mixture was heated to reflux and refluxed for 3 hours to complete the reaction. The organic phase was separated, extracted, dried, column chromatographed, and the solvent was spin-dried to give 22.8g of white solid M2 with a yield of 87%.
(3) In a 1L three-necked flask with mechanical stirring, M2 (26.2 g,0.1 mol) and 300mL of acetone were added to completely dissolve the mixture, a solution of KOH (11.2 g,0.2 mol) dissolved in water (50 mL) was added, o-bromobenzoyl chloride (22g, 0.1 mol) was slowly added dropwise to the flask, solids were gradually precipitated from the flask, and the reaction was completed by reacting at room temperature for 2 hours after completion of the dropwise addition. Adjusting to neutrality, separating an organic phase, extracting, drying, performing column chromatography, and spin-drying the solvent to obtain 33.9g of white solid M3 with the yield of 76%.
(4) Adding M3 (44.6 g,0.1 mol) into a 1L three-necked flask, adding 200mL of glycol ether under the protection of nitrogen, gradually heating to reflux, gradually dissolving the solid, magnetically stirring, keeping the temperature and reacting for 3 hours, and finishing the reaction. The organic phase was separated, extracted, dried, column chromatographed and the solvent dried to give 34.7g of a pale pink solid M4 in 81% yield.
(5) Under the protection of nitrogen, 800mL of M4 (42.8g, 0.1mol) and 800mL of anhydrous THF were added to a 2L three-necked flask, the flask was cooled to-78 ℃, a 2.5M n-hexane solution of n-butyllithium (100mL, 0.25mol) was slowly added dropwise with stirring for about 30mins, the dropping funnel was flushed with 50mL of anhydrous THF, and the temperature was maintained for 1.5 hours to obtain a reaction solution of M5. Slowly dripping sulfur dichloride (1695 ml, 0.25mol) in a low-temperature system at-78 ℃, then flushing a dropping funnel by using a small amount of anhydrous THF, preserving the temperature for 1 hour after finishing dripping, slowly heating to room temperature, stirring at room temperature for reacting for 4 hours, and finishing the reaction. Adjusting to neutrality, separating an organic phase, extracting, drying, performing column chromatography, and spin-drying the solvent to obtain 26.6g of white solid P1 with the yield of 58%.
Product MS (m/e): 300.07; elemental analysis (C) 19 H 12 N 2 S): theoretical value C:75.97%, H:4.03%, N:9.33 percent; found value C:76.08%, H:4.11%, N:9.16 percent.
Example 2: synthesis of ligand P2
Referring to the synthetic procedure of example 1, except for replacing o-bromobenzoyl chloride with 2-bromo-4-methylbenzoyl chloride in step (3), the other starting materials and procedures were the same as in example 1 to obtain ligand P2.
Product MS (m/e): 314; elemental analysis (C) 20 H 14 N 2 S): theoretical value C:76.40%, H:4.49%, N:8.91 percent; found value C:76.49%, H:4.56%, N:8.88 percent.
Example 3: synthesis of ligand P3
Referring to the synthetic procedure of example 1, except for replacing 2-bromoaniline with 2-bromo-4-methylaniline in step (1), the other starting materials and procedures were the same as in example 1, to obtain ligand P3.
Product MS (m/e): 314; elemental analysis (C) 20 H 14 N 2 S): theoretical value C:76.40%, H:4.49%, N:8.91 percent; found value C:76.49%, H:4.56%, N:8.88 percent.
Example 4: synthesis of ligand P4
Referring to the synthetic procedure of example 1, except for replacing 2-fluoronitrobenzene with 2-fluoro-5-isopropylnitrobenzene in step (1), the other raw materials and procedures were the same as in example 1, to obtain ligand P4.
Product MS (m/e): 342; elemental analysis (C) 22 H 18 N 2 S): theoretical value C:77.16%, H:5.30%, N:8.18 percent; found value C:71.09%, H:5.36%, N:8.12 percent.
Example 5: synthesis of ligand P5
Referring to the synthetic procedure of example 1, except that 4-bromo-dibenzofuran-3-carbonyl chloride was used instead of o-bromobenzoyl chloride in step (3), the other raw materials and procedures were the same as in example 1 to obtain ligand P5.
Product MS (m/e): 390; elemental analysis (C) 25 H 14 N 2 SO): theoretical value C:76.90%, H:3.61%, N:7.17 percent; measured value C:77.02%, H:3.56%, N:7.12 percent.
Example 6: synthesis of ligand P6
The specific experimental steps are as follows: in a 500mL three-necked flask equipped with mechanical stirring, the system was made to be an inert atmosphere by vacuum-nitrogen charging cycle three times, ligand P3 (31g, 0.1mol), DMSO-D6 (340g, 4.04mol), potassium tert-butoxide (1.12g, 10mmol) were added, under the protection of nitrogen, heated to 120 ℃, sufficiently stirred for reaction for 10 hours, the reaction system was cooled to room temperature, added to a large amount of deionized water, extracted three times with 300mL of ethyl acetate, the organic phases were combined, washed twice with saturated saline, the organic phase was separated, extracted, dried, column-chromatographed, and the solvent was spin-dried to obtain 28.5g of white nuclear magnetic solid P6, yield 90%, and deuterium substitution rate of 97.5% was confirmed by analysis.
Example 7: synthesis of Compound III-1
The reaction formula is as follows:
the specific experimental steps are as follows:
(1) In a 500mL three-neck flask equipped with a mechanical stirring device, a reflux condensing device and a nitrogen protection device, sequentially adding: ligand P1 (25mmmol, 7.5 g), iridium trichloride hydrate (10mmol, 3.35g), 90mL of ethylene glycol monoethyl ether and 30mL of distilled water. Vacuumizing and filling N 2 Repeating the above steps for 5 times to remove oxygen in the system. Heated to 110 ℃ under reflux for 24 hours. After natural cooling, 10mL of distilled water is added, and the mixture is shaken, filtered, washed with water and washed with ethanol. Vacuum drying gave 5.9g of crude M6 as a yellow solid in 71% yield.
(2) To a 250mL three-necked flask equipped with a magnetic stirring and reflux condenser, the above intermediate M6 (5 mmol,8.3 g), acetylacetone (25mmol, 2.5 g, 2.6 mL), and anhydrous Na were added in this order 2 CO 3 (22mmol, 2.35 g) and 100mL of ethylene glycol monoethyl ether. Vacuumizing and filling N 2 Repeating the above steps for 5 times to remove oxygen in the system. N is a radical of hydrogen 2 Heated to reflux in an oil bath at 120 ℃ for 24 hours under protection. Naturally cooling to room temperature, filtering, washing with water, n-hexane and diethyl ether in sequence, and drying to obtain a yellow crude product. By CH 2 Cl 2 Column separation after dissolution, eluent CH 2 Cl 2 The solvent was then drained to give 7.4 g of a yellow powder in 83% yield.
Product MS (m/e): 890; elemental analysis (C) 43 H 29 IrN 4 O 2 S 2 ): theoretical value C:58.03%, H:3.28%, N:6.29 percent; found value C:58.01%, H:3.32%, N:6.40 percent.
Example 8: synthesis of Compound I-1
The reaction formula is as follows:
the specific experimental steps are as follows: ir (acac) was added sequentially to a 250ml three-necked flask equipped with a magnetic stirring and reflux condenser 3 (10mmol, 4.9 g), ligand P1 (40mmol, 12 g), and 150mL of glycerol. Vacuumizing and filling N 2 Repeating the steps for 5 times to remove oxygen in the system. N is a radical of 2 The mixture was heated to reflux in an oil bath at 190 ℃ for 24 hours under protection. Naturally cooling to room temperature, filtering, washing with water, n-hexane and diethyl ether in sequence, and drying to obtain a yellow crude product. By CH 2 Cl 2 After dissolution, column separation, eluent CH 2 Cl 2 The solvent was then drained to give 4.5 g of a yellow powder with a yield of 41%.
Product MS (m/e): 1090; elemental analysis (C) 57 H 33 IrN 6 S 3 ): theoretical value C:62.79%, H:3.05%, N:7.71 percent; found value C:62.85%, H:3.11%, N:7.64 percent.
Example 9: synthesis of Compound II-2
The reaction formula is as follows:
the specific experimental steps are as follows:
(1) In a 100mL three-necked flask equipped with a mechanical stirring device, a reflux condenser and a nitrogen gas protector, phenylpyridine (15mmol, 2.5mL), iridium trichloride hydrate (6mmol, 2.01g), 45mL of ethylene glycol monoethyl ether and 15mL of distilled water were sequentially added. Vacuumizing, filling N 2 Repeating the steps for five times to remove oxygen in the system. Heated to 110 ℃ under reflux for 24 hours. Natural coolingAfter cooling, 10mL of distilled water was added, followed by shaking, suction filtration, water washing, and ethanol washing. Vacuum drying afforded 2.6g of crude M7 as a yellow solid in 81.0% yield.
(2) In a 500mL three-necked flask equipped with a nitrogen blanket, dichloro-bridged intermediate M7 (10.7g, 10mmol) was sequentially added, 150mL of dichloromethane was added, and the mixture was sufficiently stirred, then 200mL of a methanol solution of silver trifluoromethanesulfonate (6.4g, 25mmol) was added, and the mixture was stirred for 24 hours in the dark, cooled to room temperature, the formed AgCl was filtered off with celite, and the filtrate was spin-dried to obtain a yellowish solid powder. The solid was used in the next reaction without further treatment.
(3) In a 250ml three-necked flask, the solid yellowish brown (5.1g, 6.9 mmol) obtained in the above step (2) and the ligand P1 (6 g, 21mmol) were charged, then 100ml of ethanol was added, the mixture was heated under reflux for 36 hours, the reaction was cooled to room temperature, the resultant yellow solid was filtered, and this solid was dissolved in methylene chloride and subjected to column chromatography to give 10.2 g of a bright yellow solid in a yield of 64% in two steps.
Product MS (m/e): 800; elemental analysis (C) 41 H 27 IrN 4 S): theoretical value C:61.56%, H:3.40%, N:7.00 percent; found value C:61.61%, H:3.46%, N:7.05 percent.
Other specific phosphorescent compounds listed in the present invention were synthesized with reference to the above synthesis method.
Example 10: stability verification experiment
As for the known control compound GD01 and the compound III-1 obtained according to the invention, 5g of each of them was placed in a high vacuum sublimation apparatus at 6.0 x 10 -4 Sublimation was carried out at 310 ℃ under a vacuum of pascal for 20 hours, and the sublimation results are shown in table 1.
TABLE 1
As can be seen from the data in the table above, the purity of the compound III-1 provided by the invention is unchanged after sublimation, and the purity of the compound GD01 obviously decreases after sublimation. Therefore, the cyclization strategy adopted by the invention can effectively improve the thermal stability of the prepared phosphorescent material.
Example 11: preparation of OLED device
The application embodiment of the OLED device of the compound provided by the invention is as follows, the embodiment provides a group of OLED green light devices, and the structure of the device is as follows: ITO/HATCN (1 nm)/HT 01 (60 nm)/TAPC (40 nm)/DIC-TRZ: 5% phosphorescent light-emitting material compound of the present invention (40 nm)/TPBI (5 nm) ET01: QLi (1:1) (30 nm)/LiF (1 nm)/Al.
The molecular structure of each functional layer material is as follows:
preparing an OLED-1 device:
the compound III-1 prepared by the invention is selected as a phosphorescent light-emitting material, the doping concentration of the compound III-1 is 5%, and an OLED device is prepared by the following specific preparation method:
(1) Carrying out ultrasonic treatment on the glass plate coated with the ITO transparent conductive layer in a commercial cleaning agent, washing the glass plate in deionized water, ultrasonically removing oil in an acetone-ethanol mixed solvent (the volume ratio is 1: 1), baking the glass plate in a clean environment until the water is completely removed, cleaning the glass plate by using ultraviolet light and ozone, and bombarding the surface by using low-energy cationic beams;
(2) Placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to 1 × 10 -5 ～9×10 -3 Pa, performing vacuum evaporation on the anode layer film to form HATCN as a hole injection layer, wherein the evaporation rate is 0.1nm/s, and the total thickness of the evaporation film is 1nm; then, evaporating a first hole layer HT01 at the evaporation rate of 0.1nm/s and the thickness of 60nm; then evaporating a second hole transportThe evaporation rate of the layer TAPC is 0.1nm/s, and the thickness of the evaporation film is 40nm;
(3) The EML is evaporated on the hole transport layer in vacuum and used as a light emitting layer of the device, the EML comprises a main material DIC-TRZ and a dye material III-1 of the invention, the doping mass percentage concentration is 5%, an organic light emitting layer of the device is formed, the evaporation rate is 0.2nm/s, and the total evaporation film thickness is 40nm; then 5nm of TPBI is evaporated to form a hole blocking layer, and the evaporation rate is 0.1nm/s;
(4) Evaporating ET01: QLi with the mass ratio of 1:1 on the hole blocking layer to be used as an electron transport material of an electron transport layer of the device, wherein the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 30nm;
(5) LiF with the thickness of 1nm is sequentially subjected to vacuum evaporation on the electron transport layer to serve as an electron injection layer, and an Al layer with the thickness of 150nm serves as a cathode of the device. And packaging to obtain the OLED-1 device.
Preparing OLED-2-OLED-3 devices:
according to the preparation method of the OLED-1 device, only the doping concentration of the dye material III-1 in the host material DIC-TRZ in the step (3) is changed from 5% to 8% and 10% respectively, and OLED-2 and OLED-3 devices are prepared.
The performance of the devices OLED-1 to OLED-3 prepared above was tested, and the results of testing the performance of each device are detailed in Table 2.
TABLE 2
Comparing the detection results of the three light emitting devices, it can be seen that the performance of the light emitting device OLED-2 is the best, that is, when the doping concentration is about 8%, the brightness is the highest, and the efficiency is also the highest.
Preparing OLED-4-OLED-10 devices:
according to the preparation method of the OLED-1 device, the dye material III-1 in the step (3) is respectively replaced by the compounds I-1, I-2, I-5, II-2, II-1, II-39 and III-2, and the doping concentration in the host material DIC-TRZ is 8 percent, so that the OLED-4-OLED-10 device is prepared.
The comparative device 1 is prepared by using a compound GD01 with a known structure as a dye material to replace the dye material III-1 in the OLED-1 device, and the doping concentration in the host material DIC-TRZ is 8%.
The performance of the devices OLED-2, OLED-4-OLED-10 and the comparative devices are tested, and the performance test results of the devices are shown in Table 3.
TABLE 3
From the above results, compared with GD01 and III-1, the stability of the compound itself is improved, and the lifetime of the corresponding device is significantly prolonged while the light emitting efficiency is further improved. And compounds of different coordination modes: on one hand, the colors of the emitted light can be adjusted, the photoelectric properties of the corresponding devices and the service lives of the devices are also obviously influenced, the light emitting properties of the compound and the wide adjustability of device data are shown, and solutions can be provided according to different customer requirements. Therefore, the phosphorescent material provided by the invention can effectively solve the problems of the commonly used phosphorescent material in the aspects of color purity, luminous efficiency, service life and the like, and an organic electroluminescent device prepared by using the phosphorescent material provided by the invention has the excellent performances of high purity, high brightness and high efficiency.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that modifications and improvements can be made thereto without departing from the scope of the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (11)
1. An organic electrophosphorescent material, characterized by having a structure represented by general formula (I):
wherein:
R 1 ～R 11 each independently selected from hydrogen atom and C 1 ～C 5 Alkyl of (C) 1 ～C 5 Deuterated alkyl, phenyl, fluorine atom, alkoxy containing 1-5C atoms and trifluoromethyl; or, R 1 ～R 11 Wherein adjacent substituent groups form a fused ring structure through bridging, the fused ring structure is a substituted or unsubstituted benzene ring, and the substituent group adopted for substitution is C 1 ～C 5 Alkyl, phenyl, benzo groups;
l is a group of formula L1 or formula L2:
wherein:
in the formula L1, R 12 ～R 19 Each independently selected from hydrogen atom, C 1 ～C 5 Alkyl group, fluorine atom, phenyl group, C 1 ～C 5 Deuterated alkyl of (a); or, R 12 ～R 19 Wherein adjacent substituent groups form a fused ring structure through bridging, the fused ring structure is a substituted or unsubstituted benzene ring, and the substituent group adopted for substitution is C 1 ～C 5 Alkyl, phenyl, benzo, pyrido substituted with alkyl having 1 to 5C atoms, pyrido substituted with deuterated alkyl having 1 to 5C atoms;
in the formula L2, R 20 ～R 26 Each independently selected from hydrogen atom, deuterium atom, C 1 ～C 5 Alkyl groups of (a);
n is 1, 2 or 3.
2. The phosphorescent light-emitting material of claim 1, wherein the phosphorescent light-emitting material is a compound represented by formula I or formula II or formula III:
wherein m is 1 or 2.
3. A phosphorescent light-emitting material according to claim 1 or 2, wherein the phosphorescent light-emitting material is optionally selected from compounds represented by the following structural formulae:
4. use of a phosphorescent light emitting material according to any one of claims 1 to 3 in the preparation of an organic electroluminescent device.
5. The use according to claim 4, wherein the phosphorescent light-emitting material is used as a light-emitting material in an organic electroluminescent device.
6. The use according to claim 5, wherein the phosphorescent light-emitting material is doped in the host material at a concentration of 3 to 12%.
7. An organic electroluminescent device comprising a light-emitting layer comprising the phosphorescent light-emitting material according to any one of claims 1 to 3.
8. The organic electroluminescent device according to claim 7, wherein the light-emitting layer comprises a host material and a dye material, and the dye material comprises the phosphorescent light-emitting material according to any one of claims 1 to 3.
9. The device of claim 8, wherein the doping concentration of the phosphorescent material in the host material is 3-12%.
10. A display device comprising the organic electroluminescent element as claimed in any one of claims 7 to 9.
11. A lighting device comprising the organic electroluminescent element as claimed in any one of claims 7 to 9.
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