CN116925149A - Compound, organic electroluminescent device and electronic equipment - Google Patents
Compound, organic electroluminescent device and electronic equipment Download PDFInfo
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- CN116925149A CN116925149A CN202210339908.XA CN202210339908A CN116925149A CN 116925149 A CN116925149 A CN 116925149A CN 202210339908 A CN202210339908 A CN 202210339908A CN 116925149 A CN116925149 A CN 116925149A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 286
- 239000010410 layer Substances 0.000 claims description 83
- 125000004429 atom Chemical group 0.000 claims description 81
- 239000000463 material Substances 0.000 claims description 36
- -1 cyano, isocyano, sulfone Chemical compound 0.000 claims description 27
- 238000005859 coupling reaction Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 26
- 229910052717 sulfur Inorganic materials 0.000 claims description 25
- 229910052760 oxygen Inorganic materials 0.000 claims description 22
- 125000004122 cyclic group Chemical group 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 18
- 239000002346 layers by function Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 239000004215 Carbon black (E152) Substances 0.000 claims description 11
- 229930195733 hydrocarbon Natural products 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- 125000004414 alkyl thio group Chemical group 0.000 claims description 9
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims description 9
- 125000003396 thiol group Chemical class [H]S* 0.000 claims description 9
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 claims description 6
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 6
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 229910052805 deuterium Inorganic materials 0.000 claims description 6
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 claims description 6
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000000304 alkynyl group Chemical group 0.000 claims description 5
- 125000003368 amide group Chemical group 0.000 claims description 5
- 150000004820 halides Chemical class 0.000 claims description 5
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910052711 selenium Inorganic materials 0.000 claims description 4
- BPMFPOGUJAAYHL-UHFFFAOYSA-N 9H-Pyrido[2,3-b]indole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=N1 BPMFPOGUJAAYHL-UHFFFAOYSA-N 0.000 claims description 3
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 claims description 3
- WIUZHVZUGQDRHZ-UHFFFAOYSA-N [1]benzothiolo[3,2-b]pyridine Chemical compound C1=CN=C2C3=CC=CC=C3SC2=C1 WIUZHVZUGQDRHZ-UHFFFAOYSA-N 0.000 claims description 3
- RFRXIWQYSOIBDI-UHFFFAOYSA-N benzarone Chemical compound CCC=1OC2=CC=CC=C2C=1C(=O)C1=CC=C(O)C=C1 RFRXIWQYSOIBDI-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 239000004334 sorbic acid Substances 0.000 claims description 3
- 125000005580 triphenylene group Chemical group 0.000 claims description 3
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 102
- 230000015572 biosynthetic process Effects 0.000 description 35
- 238000003786 synthesis reaction Methods 0.000 description 35
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 34
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 31
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 239000002994 raw material Substances 0.000 description 26
- 239000012043 crude product Substances 0.000 description 23
- 239000012044 organic layer Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 19
- 238000004440 column chromatography Methods 0.000 description 17
- 239000003480 eluent Substances 0.000 description 17
- 239000003208 petroleum Substances 0.000 description 17
- 229910052786 argon Inorganic materials 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 238000001816 cooling Methods 0.000 description 14
- 239000011669 selenium Substances 0.000 description 14
- 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 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 238000002347 injection Methods 0.000 description 10
- 239000007924 injection Substances 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 10
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 10
- 239000007858 starting material Substances 0.000 description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 9
- 239000011591 potassium Substances 0.000 description 9
- 229910052700 potassium Inorganic materials 0.000 description 9
- 238000000103 photoluminescence spectrum Methods 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 6
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 6
- 230000000903 blocking effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 description 6
- 230000005587 bubbling Effects 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000005401 electroluminescence Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- BWRRWBIBNBVHQF-UHFFFAOYSA-N 4-(3-pyridin-2-yl-1,2,4-oxadiazol-5-yl)butanoic acid Chemical compound O1C(CCCC(=O)O)=NC(C=2N=CC=CC=2)=N1 BWRRWBIBNBVHQF-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 230000005525 hole transport Effects 0.000 description 4
- 230000001976 improved effect Effects 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 description 4
- 229910000104 sodium hydride Inorganic materials 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000001194 electroluminescence spectrum Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 125000004434 sulfur atom Chemical group 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000001748 luminescence spectrum Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 238000001228 spectrum Methods 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
- 238000012546 transfer Methods 0.000 description 2
- ROMPPAWVATWIKR-UHFFFAOYSA-N 4-[3-(4-chlorophenyl)-1,2,4-oxadiazol-5-yl]butanoic acid Chemical compound O1C(CCCC(=O)O)=NC(C=2C=CC(Cl)=CC=2)=N1 ROMPPAWVATWIKR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical group [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003190 augmentative effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical group [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 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 1
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- KGYLMXMMQNTWEM-UHFFFAOYSA-J tetrachloropalladium Chemical compound Cl[Pd](Cl)(Cl)Cl KGYLMXMMQNTWEM-UHFFFAOYSA-J 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
- C07F15/006—Palladium compounds
-
- 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 System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
- C07F15/0086—Platinum compounds
-
- 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
-
- 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
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The application provides a compound, an organic electroluminescent device and electronic equipment, wherein the compound has a structure shown as a formula I, and M represents Pd (II) or Pt (II); the compound contributes to the organic electroluminescent device exhibiting excellent color purity and stability.
Description
Technical Field
The application relates to a compound, an organic electroluminescent device and electronic equipment, and belongs to the technical field of organic electroluminescence.
Background
In the 60 s of the 20 th century, 400V applied to an anthracene single crystal plate was observed by Pope et al, new york university in the united states, which was the first report of the phenomenon of organic electroluminescence. After 20 years, researchers invented a vacuum evaporation technique to prepare an anthracene film, and observed blue light with an External Quantum Efficiency (EQE) of 0.03% at a drive voltage of 30V. The organic electroluminescent device studied in the early stage has the defects of low carrier injection efficiency, poor film quality, large device working voltage and the like, and has low practical application value. Until 1987, C.W.Tang et al utilized octahydroxyquinoline aluminum as the light-emitting layer, aromatic amine compounds as the hole-transporting layer, and aluminum magnesium alloy as the cathode to obtain a sandwich-type green light device with high luminous efficiency. Organic light emitting diodes (Organic Light EmittingDiode, abbreviated to OLEDs) have been a research focus in the field of organic photovoltaics as a device that emits light by current driving. The power for promoting the final popularization and application of the OLED technology is characterized by simple process, low energy consumption, low cost, high response speed, capability of realizing flexible display, large-area display and the like.
In the field of OLED materials, the phosphorescent OLED luminescent layer doped material is developed rapidly and mature, and particularly, the energy use efficiency of 100% can be achieved by introducing heavy metal atoms such as iridium or platinum to realize the transition from singlet excitons to triplet excitons, so that the phosphorescent luminescent material is a luminescent material which is researched in relatively large quantity in the industry and academia.
In recent years, phosphorescent OLED materials based on platinum (II) are gradually developed and have achieved better research results. However, the phosphorescent material of platinum (II) still has defects such as an excessively broad luminescence spectrum and poor stability.
Disclosure of Invention
The embodiment of the application provides a compound, an organic electroluminescent device and electronic equipment, and the special structure of the compound enables the compound to be used as a phosphorescence luminescent material to show excellent color purity and stability.
In a first aspect, embodiments of the present application provide a compound having a structure according to formula I,
Z 1 、Z 2 、Z 3 z is as follows 4 Independently selected from single bond, O, S or Se;
X 1 、X 2 、X 3 x is as follows 4 Any two of them are N, and the other two are C;
Q 1 、Q 2 、Q 3 q and 4 independently selected from single bond, O, S, se, -CR 1 R 2 、-C＝O、-SiR 1 R 2 、-GeR 1 R 2 、-NR 1 、-BR 1 、-AlR 1 、-PR 1 、-AsR 1 、-S＝O、-SO 2 、-Se＝O、-SeO 2 、-BiR 1 Or a group of formula a, and Q 1 、Q 2 、Q 3 Q and 4 at least one of them is a group of the formula A, in which L n Selected from L 5 、L 6 、L 7 L and 8 ，Y n 、Y m independently selected from Y 1 、Y 2 、Y 3 、Y 4 、Y 5 、Y 6 、Y 7 Y is as follows 8 One of them;
L 1 、L 2 、L 3 、L 4 、L 5 、L 6 、L 7 l and 8 independently selected from substituted or unsubstituted 3 to 50 membered cyclic groups;
Y 1 、Y 2 、Y 3 、Y 4 、Y 5 、Y 6 、Y 7 y is as follows 8 Independently selected from O, S, se, -CR 1 R 2 、-C＝O、-SiR 1 R 2 、-GeR 1 R 2 、-NR 1 、-BR 1 、-AlR 1 、-PR 1 、-AsR 1 ,-S＝O、-SO 2 、-Se＝O、-SeO 2 、-BiR 1 A substituted or unsubstituted 3-to 50-membered cyclic group and Y n 、Y m Not both benzene rings;
wherein R is 1 、R 2 Independently selected from hydrogen, deuterium, halogen, hydroxy, thiol, nitro, cyano, isocyano, sulfone, hydroxylamine, carboxyl, carbonyl, or one of the following substituted or unsubstituted groups: C6-C48 monocyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbon, C3-C48 monocyclic heteroaromatic hydrocarbon or polycyclic heteroaromatic hydrocarbon, C1-C36 alkyl, C2-C36 heterocycloalkyl, C2-C36 alkenyl, C2-C36 alkynyl, amino, C1-C36 alkoxy, C1-C36 alkylthio, amido, silicon base and boron base.
As can be seen from the above formula 1, the compound provided by the present application is a metal complex, specifically, the compound is a tetradentate coordination compound of metal Pt (II) and metal Pd (II). In the compound shown in the formula I, the two ligands form a closed loop structure and Q 1 、Q 2 、Q 3 Q and 4 at least one of which is a group of formula A. On the one hand, the structure narrows the luminescence spectrum of the compound when the compound is used as a luminescent material, and further, the compound has excellent color purity; on the other hand, the structure also suppresses the vibration of the compound molecules to some extent, so that the stability is improved.
In one possible implementation, the compound has a structure represented by formula II or formula III,
in the formula II, X 11 X is as follows 12 Is L 1 Is a ring-forming atom, X 21 、X 22 X is as follows 23 Is L 2 Is a ring-forming atom, X 31 、X 32 X is as follows 33 Is L 3 Is a ring-forming atom, X 41 X is as follows 42 Is L 4 Ring-forming atoms of Q 1 、Q 3 Q and 4 independently selected from single bond, O, S, se, -CR 1 R 2 、-C＝O、-SiR 1 R 2 、-GeR 1 R 2 、-NR 1 、-BR 1 、-AlR 1 、-PR 1 、-AsR 1 、-S＝O、-SO 2 、-Se＝O、-SeO 2 、-BiR 1 ；
In the formula III, X 11 、X 12 X is as follows 13 Is L 1 Is a ring-forming atom, X 21 、X 22 X is as follows 23 Is L 2 Is a ring-forming atom, X 31 、X 32 X is as follows 33 Is L 3 Is a ring-forming atom, X 41 、X 42 X is as follows 43 Is L 4 Ring-forming atoms of Q 1 Q and 4 independently selected from single bond, O, S, se, -CR 1 R 2 、-C＝O、-SiR 1 R 2 、-GeR 1 R 2 、-NR 1 、-BR 1 、-AlR 1 、-PR 1 、-AsR 1 、-S＝O、-SO 2 、-Se＝O、-SeO 2 、-BiR 1 。
In one possible implementation, the compound has a structure as shown in any one of M1-M40.
In one possible implementation, the compound has a structure as shown in any one of P1 to P200, S1 to S200, T1 to T200, E1 to E200, F1 to F200, K1 to K200, G1 to G200, R1 to R200, and X1 to X8.
In one possible implementation, the compound is obtained by a process comprising reacting a compound represented by formula I-1 with a halide of metal M.
In one possible implementation, the compound of formula I-1 is prepared by a process comprising:
reacting a raw material comprising a compound represented by formula 1 with a compound represented by formula 2 to obtain a compound represented by formula 3;
Reacting a raw material comprising a compound represented by formula 3 with a compound represented by formula 4 to obtain a compound represented by formula 5;
reacting a raw material comprising a compound represented by formula 5 with a compound represented by formula 6 to obtain a compound represented by formula 7;
reacting a raw material comprising a compound shown in a formula 7 to obtain a compound shown in a formula I-1;
or alternatively, the process may be performed,
reacting a raw material comprising a compound represented by formula 1 with a compound represented by formula 2 to obtain a compound represented by formula 3;
reacting a raw material comprising a compound represented by formula 3 with a compound represented by formula 8 to obtain a compound represented by formula 7;
reacting a starting material comprising a compound represented by formula 7 to obtain a compound represented by formula I-1.
In one possible implementation, the compound of formula I-1 is prepared by a process comprising:
reacting a compound shown in a formula a-1 with a compound shown in a formula a-2 to obtain a compound shown in a formula b 1;
reacting a compound shown in a formula a-3 with a compound shown in a formula a-4 to obtain a compound shown in a formula b 2;
reacting a compound shown in a formula b1, a compound shown in a formula b2 and a compound shown in a formula a5 to obtain a compound shown in a formula b 3;
Reacting a compound represented by the formula b3 with a compound E to obtain a compound represented by I-1.
A second aspect of an embodiment of the present application provides a method for preparing a compound of the first aspect, comprising the steps of:
the compound shown in the formula I-1 is obtained by reacting with a halide of metal M.
In one possible implementation, the compound of formula I-1 is prepared by a process comprising:
reacting a raw material comprising a compound represented by formula 1 with a compound represented by formula 2 to obtain a compound represented by formula 3;
reacting a raw material comprising a compound represented by formula 3 with a compound represented by formula 4 to obtain a compound represented by formula 5;
reacting a raw material comprising a compound represented by formula 5 with a compound represented by formula 6 to obtain a compound represented by formula 7;
reacting a raw material comprising a compound shown in a formula 7 to obtain a compound shown in a formula I-1;
or alternatively, the process may be performed,
reacting a raw material comprising a compound represented by formula 1 with a compound represented by formula 2 to obtain a compound represented by formula 3;
reacting a raw material comprising a compound represented by formula 3 with a compound represented by formula 8 to obtain a compound represented by formula 7;
reacting a starting material comprising a compound represented by formula 7 to obtain a compound represented by formula I-1.
In one possible implementation, the compound of formula I-1 is prepared by a process comprising:
reacting a compound shown in a formula a-1 with a compound shown in a formula a-2 to obtain a compound shown in a formula b 1;
reacting a compound shown in a formula a-3 with a compound shown in a formula a-4 to obtain a compound shown in a formula b 2;
reacting a compound shown in a formula b1, a compound shown in a formula b2 and a compound shown in a formula a5 to obtain a compound shown in a formula b 3;
reacting a compound represented by the formula b3 with a compound E to obtain a compound represented by I-1.
The preparation method provided by the embodiment of the application can prepare the compound shown in the formula I in a safer and milder mode, and has higher yield.
A third aspect of an embodiment of the present application provides a functional layer comprising a compound of the foregoing first aspect.
According to a fourth aspect of embodiments of the present application there is provided a mixture comprising at least one compound of the first aspect.
The present application is not limited to the specific composition of the mixture, and the mixture referred to in the present application is any one as long as the compound of the aforementioned first aspect is included. Since the mixture has the aforementioned compounds, the mixture has advantages of improving color purity and stability in the field of organic electroluminescence.
A fifth aspect of an embodiment of the present application also provides an organic electroluminescent device comprising a light-emitting layer comprising a compound according to any one of the preceding first aspects.
The organic electroluminescent device of the embodiment of the application has excellent color purity and device stability because the compound is used as a phosphorescence luminescent material.
It is understood that the organic electroluminescent device according to the embodiments of the present application further includes other functional layers, such as a cathode layer, an anode layer, an electron transport layer, a hole transport layer, etc., in addition to the above-described light emitting layer.
In one possible implementation, the light-emitting layer of the organic electroluminescent device according to an embodiment of the present application consists only of the compound of the aforementioned first aspect.
In one possible implementation manner, the light-emitting layer of the organic electroluminescent device according to an embodiment of the present application includes a host material and a dye, where the dye is a compound of the foregoing first aspect.
In this implementation, the dye receives excitons from the host material and itself undergoes transition from singlet excitons to triplet excitons, thereby emitting phosphorescence to achieve efficient use of energy.
In one possible implementation manner, the light-emitting layer of the organic electroluminescent device according to an embodiment of the present application includes a host material, a sensitizer, and a dye, and one of the sensitizer and the dye is a compound of the foregoing first aspect.
Specifically, when the aforementioned compound is used as a sensitizer, it receives excitons from the host material and passes throughEnergy transfer and Dexter energy transfer singlet excitons and triplet excitons to the dye, sensitizing the dye to phosphorescence emission.
When the compound is used as a dye, the compound receives excitons from a sensitizer and generates transition from singlet excitons to triplet excitons by itself, and phosphorescence is emitted to realize efficient energy utilization.
The organic electroluminescent device according to the embodiment of the application, because the compound of the first aspect is included in the light-emitting layer, the characteristics of narrow spectrum and high stability of the compound are beneficial to improving the color purity and stability of the organic electroluminescent device, and particularly, the stability is mainly represented by remarkable inhibition of the efficiency roll-off of the organic electroluminescent device, regardless of the specific composition mode of the light-emitting layer.
In one possible implementation, the dye is present in the light-emitting layer in an amount of 0.1 to 20% by mass.
In one possible implementation, the mass percentage of the host material in the light-emitting layer is 50-95%, the mass percentage of the sensitizer in the light-emitting layer is 1-30%, and the mass percentage of the dye in the light-emitting layer is 0.1-20%.
In one possible implementation, the host material is selected from at least one of carbazole, triphenylene, benzothiophene, benzofuran, dibenzothiophene, dibenzofuran, azacarbazole, azatriphenylene, azabenzothiophene, azabenzofuran, azadibenzothiophene, azadibenzofuran.
A sixth aspect of an embodiment of the present application provides an electronic device, including the organic electroluminescent device of the sixth aspect. The electronic device has excellent color purity and stability.
Drawings
FIG. 1 is a photoluminescence spectrum of the compound Pt-1 of synthetic example 1 of the present application in methylene chloride solution;
FIG. 2 is a photoluminescence spectrum of the compound Pt-2 of synthetic example 2 of the present application in methylene chloride solution;
FIG. 3 is a photoluminescence spectrum of the compound Pt-3 of synthetic example 3 of the present application in methylene chloride solution;
FIG. 4 is a photoluminescence spectrum of the compound Pt-4 of synthetic example 4 of the present application in methylene chloride solution;
FIG. 5 is an electroluminescence spectrum of an organic electroluminescent device of device example 1;
fig. 6 is an external quantum efficiency-luminance curve of the organic electroluminescent device of device example 1.
Detailed Description
The terminology used in the description of the embodiments of the application herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application, as will be described in detail with reference to the accompanying drawings.
Currently, mainstream tetradentate platinum (II) complex phosphorescent materials and tetradentate palladium (II) complex phosphorescent materials mainly adopt carbon, nitrogen, oxygen, sulfur, phosphorus and other atoms capable of providing lone pair electrons or atoms capable of forming covalent bonds with platinum (II) atoms and palladium (II) atoms for coordination. At present, the arrangement and combination of coordination atoms and the ligand constitution modes of the phosphorescent light emitting materials are different, and the main bonding modes comprise single bond bonding, nitrogen atom bonding, oxygen atom bonding and the like, and the conjugation mode is limited to a certain extent. In application, although the OLED devices comprising the phosphorescent materials have higher luminous efficiency, the defects of half-width and poor stability of the OLED devices also lead to a certain limit on the commercial application of the phosphorescent materials.
Based on this, the first aspect of the present embodiment provides a compound having a structure shown in formula I,
in the formula I, M represents Pd (II) or Pt (II);
Z 1 、Z 2 、Z 3 z is as follows 4 Independently selected from single bond, O, S or Se;
X 1 、X 2 、X 3 x is as follows 4 Any two of them are N, and the other two are C;
Q 1 、Q 2 、Q 3 q and 4 independently selected from single bond, O, S, se, -CR 1 R 2 、-C＝O、-SiR 1 R 2 、-GeR 1 R 2 、-NR 1 、-BR 1 、-AlR 1 、-PR 1 、-AsR 1 ,-S＝O、-SO 2 、-Se＝O、-SeO 2 、-BiR 1 Or a group of formula a, and Q 1 、Q 2 、Q 3 Q and 4 at least one of them is a group of formula a, wherein L n Selected from L 5 、L 6 、L 7 L and 8 ，Y n 、Y m independently selected from Y 1 、Y 2 、Y 3 、Y 4 、Y 5 、Y 6 、Y 7 Y is as follows 8 One of them;
L 1 、L 2 、L 3 、L 4 、L 5 、L 6 、L 7 l and 8 independently selected from substituted or unsubstituted 3 to 50 membered cyclic groups;
Y 1 、Y 2 、Y 3 、Y 4 、Y 5 、Y 6 、Y 7 y is as follows 8 Independently selected from O, S, se, -CR 1 R 2 、-C＝O、-SiR 1 R 2 、-GeR 1 R 2 、-NR 1 、-BR 1 、-AlR 1 、-PR 1 、-AsR 1 ,-S＝O、-SO 2 、-Se＝O、-SeO 2 、-BiR 1 A substituted or unsubstituted 3-to 50-membered cyclic group and Y n 、Y m Not both benzene rings;
wherein R is 1 、R 2 Independently selected from hydrogen, deuterium, halogen, hydroxy, thiol, nitro, cyano, isocyano, sulfone, hydroxylamine, carboxyl, carbonyl, or one of the following substituted or unsubstituted groups: C6-C48 monocyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbon, C3-C48 monocyclic heteroaromatic hydrocarbon or polycyclic heteroaromatic hydrocarbon, C1-C36 alkyl, C2-C36 heterocycloalkyl, C2-C36 alkenyl, C2-C36 alkynyl, amino, C1-C36 alkoxy, C1-C36 alkylthio, amido, silicon base and boron base.
According to formula I, the above-mentioned compounds in the embodiments of the present application are metal tetradentate complexes, wherein the metal coordinating atom M is Pt (II) or Pd (II).
In the compound shown in the formula I, Q 1 、Q 2 、Q 3 Q and 4 at least one bridging group of formula A for linking L 1 ～L 4 Wherein Y is a cyclic group adjacent to two of the cyclic groups n 、Y m Is bonded to two adjacent cyclic groups at one end, Y n 、Y m Respectively with the other end of the cyclic group L n Is bonded to the ring-forming atom of (c). For example, when the number of bridging groups represented by formula A is 4 (i.e., Q 1 、Q 2 、Q 3 Q and 4 all of which are bridging groups of formula A), based on the composition of formula A, in one embodiment the 4 bridging groups may each be-Y 1 -L 5 -Y 2 -、-Y 3 -L 6 -Y 4 -、-Y 5 -L 7 -Y 6 -、-Y 7 -L 8 -Y 8 -。Y 1 ～Y 8 L and 5 ～L 8 each independently selected within the above ranges, so that when the number of bridging groups represented by formula a in the compound represented by formula I is greater than 1, each bridging group may be the same or different.
L 1 、L 2 、L 3 、L 4 、L 5 、L 6 、L 7 L and 8 independently selected from substituted or unsubstituted 3 to 50 membered cyclic groups, the 3 to 50 membered cyclic groups of the application mean groups consisting of 3 to 50 ring membersThe cyclic group, which may be an aromatic (hetero) ring or an aliphatic (hetero) ring, is not particularly limited in the present application. It should be noted that due to X 1 、X 2 、X 3 X is as follows 4 Any two of which are N, and thus L 1 、L 2 、L 3 、L 4 In which there are two nitrogen-containing heterocycles and the nitrogen atom is a cyclic group L (L 1 ～L 4 Two of which) are linked via Z (Z) 1 ～Z 4 One of which) is connected to M. Of these two nitrogen-containing heterocycles, of course, in addition to X (X 1 ～X 4 One of them), the remaining ring-forming atoms may be a nitrogen atom, a carbon atom, an oxygen atom, a sulfur atom, a silicon atom, a germanium atom, a phosphorus atom, an arsenic atom, a selenium atom, a boron atom, a bismuth atom or the like. And L is 1 ～L 4 In the other two cyclic groups of (2), except by Z (Z 1 ～Z 4 One of them) is linked to M and a carbon atom X (X) 1 ～X 4 One of them), the remaining ring-forming atoms may be other common ring-forming atoms such as nitrogen atom, carbon atom, oxygen atom, sulfur atom, etc. Furthermore, the application defines L 5 、L 6 、L 7 L and 8 the ring-forming atoms in (a) may be other common ring-forming atoms such as nitrogen atom, carbon atom, oxygen atom, sulfur atom, etc.
When the above-mentioned groups of the present application have substituents, the present application is not limited to the number, positions and specific types of substituents, and the substituents may be deuterium, halogen, hydroxy, amino, alkoxy, nitro, cyano, (halo) hydrocarbon, aryl, heteroaryl, carbonyl, carboxyl, ester group and the like, for example.
It should be noted that "-" in the groups according to the present application is a compound bond and is used to represent a bonding atom. By Q 1 is-CR 1 R 2 For example, CR is shown 1 R 2 Wherein the carbon atoms are respectively with L 1 L and 2 and (5) connection.
According to the technical scheme provided by the application, the compound with the composition is used as a phosphorescence luminescent material, so that the color purity and the stability of the organic electroluminescent device can be obviously improved. The inventors have based on this phenomenonLine analysis, considered possible: in the compound of the application, two adjacent ligands form a closed loop structure and Q 1 、Q 2 、Q 3 Q and 4 at least one bridging group shown in a formula A, which is beneficial to improving the plane conjugation performance of the compound and enhancing the rigidity of the molecule. On one hand, the rigidity of the molecules is favorable for inhibiting the interaction among the molecules, and inhibiting the occurrence probability of multiple emission peaks, so that the luminous color purity is improved; on the other hand, the rigidity of the molecule can reduce the vibration of the complex molecule, reduce the non-radiative transition rate, and further exhibit excellent stability.
Further, the compound has a structure shown in formula II or formula III.
In the formula II, X 11 X is as follows 12 Is L 1 Is a ring-forming atom, X 21 、X 22 X is as follows 23 Is L 2 Is a ring-forming atom, X 31 、X 32 X is as follows 33 Is L 3 Is a ring-forming atom, X 41 X is as follows 42 Is L 4 Ring-forming atoms of Q 1 、Q 3 Q and 4 independently selected from single bond, O, S, se, -CR 1 R 2 、-C＝O、-SiR 1 R 2 、-GeR 1 R 2 、-NR 1 、-BR 1 、-AlR 1 、-PR 1 、-AsR 1 、-S＝O、-SO 2 、-Se＝O、-SeO 2 、-BiR 1 ；
In the formula III, X 11 、X 12 X is as follows 13 Is L 1 Is a ring-forming atom, X 21 、X 22 X is as follows 23 Is L 2 Is a ring-forming atom, X 31 、X 32 X is as follows 33 Is L 3 Is a ring-forming atom, X 41 、X 42 X is as follows 43 Is L 4 Ring-forming atoms of Q 1 Q and 4 independently selected from single bond, O, S, se, -CR 1 R 2 、-C＝O、-SiR 1 R 2 、-GeR 1 R 2 、-NR 1 、-BR 1 、-AlR 1 、-PR 1 、-AsR 1 、-S＝O、-SO 2 、-Se＝O、-SeO 2 、-BiR 1 。
The choice of ring-forming atoms of formula II and formula III is the same as defined above and will not be described in detail here.
In particular of formula II, Q 1 、Q 3 Q and 4 independently selected from single bond, O, S, se, -CR 1 R 2 、-C＝O、-SiR 1 R 2 、-GeR 1 R 2 、-NR 1 、-BR 1 、-AlR 1 、-PR 1 、-AsR 1 、-S＝O、-SO 2 、-Se＝O、-SeO 2 、-BiR 1 One of Q 2 Is a group of formula A, in particular-Y 1 -L 5 -Y 2 -. And L is 1 Respectively with Q 1 And Q 3 Attached ring-forming atom X 11 And X 12 Each with a ring-forming atom X 1 Ortho, L 4 Respectively with Q 4 And Q 3 Attached ring-forming atom X 41 And X 42 Each with a ring-forming atom X 4 Ortho, L 2 Intermediate and Q 1 Attached ring-forming atom X 21 With ring-forming atoms X 2 Is ortho-position and Q 2 Attached ring-forming atom X2 3 With ring-forming atoms X 2 Is meta (ring-forming atom X 22 And X is 2 Ortho-position), L 3 Intermediate and Q 4 Attached ring-forming atom X 31 With ring-forming atoms X 3 Is ortho-position and Q 2 Attached ring-forming atom X 33 With ring-forming atoms X 3 Is meta (ring-forming atom X 32 And X is 3 Ortho).
In particular of formula III, Q 1 Q and 4 independently selected from single bond, O, S, se, -CR 1 R 2 、-C＝O、-SiR 1 R 2 、-GeR 1 R 2 、-NR 1 、-BR 1 、-AlR 1 、-PR 1 、-AsR 1 、-S＝O、-SO 2 、-Se＝O、-SeO 2 、-BiR 1 One of Q 2 Q and 3 is a group of the formula A, in particular Q 2 is-Y 1 -L 5 -Y 2 -，Q 3 is-Y 3 -L 6 -Y 4 -. And L is 1 Intermediate and Q 1 Attached ring-forming atom X 11 With ring-forming atoms X 1 Is ortho-position and Q 3 Attached ring-forming atom X 13 With ring-forming atoms X 1 Is meta (ring-forming atom X 12 And X is 1 Ortho-position), L 2 Intermediate and Q 1 Attached ring-forming atom X 21 With ring-forming atoms X 2 Is ortho-position and Q 2 Attached ring-forming atom X 23 With ring-forming atoms X 2 Is meta (ring-forming atom X 22 And X is 2 Ortho-position), L 3 Intermediate and Q 4 Attached ring-forming atom X 31 With ring-forming atoms X 3 Is ortho-position and Q 2 Attached ring-forming atom X 33 With ring-forming atoms X 3 Is meta (ring-forming atom X 32 And X is 3 Ortho-position), L 4 Intermediate and Q 4 Attached ring-forming atom X 41 With ring-forming atoms X 4 Is ortho-position and Q 3 Attached ring-forming atom X 43 With ring-forming atoms X 4 Is meta (ring-forming atom X 42 And X is 4 Ortho).
Further, the compound has a structure shown in any one of M1 to M40,
wherein Ar is 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 Each independently selected from substituted or unsubstituted 5-8 membered cyclic groups, R 3 、R 4 、R 5 、R 6 、R 7 、R 8 Independently selected from hydrogen, deuterium, halogen, hydroxy, thiol, nitro, cyano, isocyano, sulfone, hydroxylamine, carboxyl, carbonyl, or one of the following substituted or unsubstituted groups: C6-C48 monocyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbon, C3-C48 monocyclic heteroaromatic hydrocarbon or polycyclic heteroaromatic hydrocarbon, C1-C36 alkyl, C2-C36 heterocycloalkyl, C2-C36 alkenyl, C2-C36 alkynyl, amino, C1-C36 Alkoxy, C1-C36 alkylthio, amido, silicon, boron.
It is to be noted that the relationship of the ring-forming atoms for bonding M through Z and the ring-forming atoms for bonding other Ar rings through Q in each Ar ring is as shown in the structural formula. For example, in M19, ar 2 In the ring for passing Z 2 Ring-forming atom X bound to M 2 And for passing through Q 1 Bonding Ar 1 The ring-forming atoms of the ring are ortho; also for example, in M32, ar 2 Ring-forming atom X in the ring for bonding M via Z2 2 And for passing through Q 2 (-O-Ar 5 -O-) is bonded to Ar thereof 3 The ring-forming atoms of the ring are meta.
In one embodiment, the compounds of the examples of the present application have the structures shown in any one of the following P1 to P200, S1 to S200, T1 to T200, E1 to E200, F1 to F200, K1 to K200, G1 to G200, R1 to R200 and X1 to X8,
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the present application is not limited to the method for synthesizing the compound having the above-described structure.
In one embodiment, the above compound comprises a compound of formula I-1 reacted with a halide of metal M;
in the formula I-1, G 1 ～G 4 Each independently selected from hydroxy, alkoxy, mercapto, alkylthio, or absent. The halogenides of the metal M of the present application are, for example, potassium tetrachloroplatinate, potassium hexachloroplatinate, potassium tetrachloropalladium, potassium hexachloropalladium, etc., which are raw materials for producing an organometallic compound.
The present application is not limited to the preparation of the compounds of formula I-1, for example,
in the preparation method, P 1 、P 2 、P 3 、P 4 、P 5 、P 6 、P 7 、P 8 Each independently selected from groups for the coupling reaction to occur, and their specific choice is according to Q 1 、Q 2 、Q 3 Q and 4 and a targeted determination. Each step of the reaction is completed through a coupling reaction, and the coupling reaction at least comprises two raw materials in the reaction formula. Taking the production of the compound represented by formula 3 as an example, the compound represented by formula 3 is obtained by reacting at least a compound represented by formula 1 and a compound represented by formula 2 as raw materials, for example, the compound represented by formula 1 and the compound represented by formula 2 are each represented by the group P 1 And P 4 The coupling reaction is carried out to generate the compound shown in the formula 3, and P 1 And P 4 View Q 1 And a targeted selection is carried out; alternatively, the group P of the compound represented by formula 1 1 And a group P of the compound represented by formula 2 4 The compounds shown in the formula 3 are respectively generated by coupling reaction with intermediate compounds, and P 1 、P 4 And intermediate compound apparent Q 1 And is selected in a targeted manner.
In addition to the above preparation methods, the preparation methods of the compounds represented by formula I-1 are as follows:
in the preparation method, P 1 、P 2 、P 3 、P 4 、P 5 、P 6 、P 7 、P 8 Each independently selected from groups for the coupling reaction to occur, and their specific choice is according to Q 1 、Q 2 、Q 3 Q and 4 and a targeted determination. Each step of the reaction is completed through a coupling reaction, and the coupling reaction at least comprises two raw materials in the reaction formula. Taking the production of the compound represented by formula 7 as an example, the compound represented by formula 7 is obtained by reacting a compound represented by at least formula 3 with a compound represented by formula 8, for example, the compound represented by formula 3 and the compound represented by formula 8 are each represented by the group P 3 And P 5 The coupling reaction is carried out to generate the compound shown in the formula 7, and P 3 And P 5 View Q 2 And a targeted selection is carried out; alternatively, the group P of the compound represented by formula 3 3 And a group P of the compound represented by formula 8 5 The compounds shown in the formula 7 are respectively generated by coupling reaction with intermediate compounds, and P 3 、P 5 And intermediate compound apparent Q 2 And is selected in a targeted manner.
In one embodiment, the compounds of formula I-1 are prepared as follows,
reacting a compound shown in a formula a-1 with a compound shown in a formula a-2 to obtain a compound shown in a formula b 1;
reacting a compound shown in a formula a-3 with a compound shown in a formula a-4 to obtain a compound shown in a formula b 2;
reacting a compound shown in a formula b1, a compound shown in a formula b2 and a compound shown in a formula a5 to obtain a compound shown in a formula b 3;
Reacting a compound represented by formula b3 with a compound E to obtain a compound represented by I-1, wherein Q 1 Q and 4 is a single bond, Q 3 Independently selected from O, S, se, -CR 1 R 2 、-C＝O、-SiR 1 R 2 、-GeR 1 R 2 、-NR 1 、-BR 1 、-AlR 1 、-PR 1 、-AsR 1 、-S＝O、-SO 2 、-Se＝O、-SeO 2 、-BiR 1 ，Q 2 Is a group of formula A;
A 1 、A 2 、A 3 a is a 4 Any atom selected from halogen, and A 1 Is greater than A 2 ，A 3 Is greater than A 4 ；
In formula a5, C 1 C 2 Independently selected from-OH, -OR 1 、-SH、-SR 1 、-SeR 1 、-CHR 1 R 2 、-CR 1 O、-SiHR 1 R 2 、-GeHR 1 R 2 、-NHR 1 、-BHR 1 、-AlHR 1 、-PHR 1 、-AsHR 1 ,-SR 1 O、-SO 2 R 1 、-SeR 1 O、-SeO 2 R 1 、-BiHR 1 A substituted or unsubstituted 3 to 50 membered cyclic group;
the compound E is selected from the group consisting of A 2 、A 4 The coupling reaction is carried out to generate Q 3 Is a compound of (a).
The following compounds are exemplified and obtained by the following preparation methods.
In the compounds, Q 1 、Q 2 、Q 3 Q and 4 two of which are single bonds, and the other two of which, one is-O-Ar-O-, the other is-N-Ar. Ar is a 5-8 membered ring.
In a second aspect, the present embodiment provides a method for preparing the foregoing compound, including the steps of:
reacting a compound represented by the formula I-1 with a halide of a metal M,
in the formula I-1, G 1 ～G 4 Each independently selected from hydroxy, alkoxy, mercapto, alkylthio, or absent.
Further, the present application is not limited to the preparation method of the compound represented by the formula I-1, for example,
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in the preparation method, P 1 、P 2 、P 3 、P 4 、P 5 、P 6 、P 7 、P 8 Each independently selected from groups for the coupling reaction to occur, and their specific choice is according to Q 1 、Q 2 、Q 3 Q and 4 and a targeted determination. Each step of the reaction is completed through a coupling reaction, and the coupling reaction at least comprises two raw materials in the reaction formula. Taking the production of the compound represented by formula 3 as an example, the compound represented by formula 3 is obtained by reacting at least a compound represented by formula 1 and a compound represented by formula 2 as raw materials, for example, the compound represented by formula 1 and the compound represented by formula 2 are each represented by the group P 1 And P 4 The coupling reaction is carried out to generate the compound shown in the formula 3, and P 1 And P 4 View Q 1 And a targeted selection is carried out; alternatively, the group P of the compound represented by formula 1 1 And a group P of the compound represented by formula 2 4 The compounds shown in the formula 3 are respectively generated by coupling reaction with intermediate compounds, and P 1 、P 4 And intermediate compound apparent Q 1 And is selected in a targeted manner.
In addition to the above preparation methods, the preparation methods of the compounds represented by formula I-1 are as follows:
in the preparation method, P 1 、P 2 、P 3 、P 4 、P 5 、P 6 、P 7 、P 8 Each independently selected from groups for the coupling reaction to occur, and their specific choice is according to Q 1 、Q 2 、Q 3 Q and 4 and a targeted determination. Each step of the reaction is completed through a coupling reaction, and the coupling reaction at least comprises two raw materials in the reaction formula. Taking the production of the compound represented by formula 7 as an example, the compound represented by formula 7 is obtained by reacting a compound represented by at least formula 3 with a compound represented by formula 8, for example, the compound represented by formula 3 and the compound represented by formula 8 are each represented by the group P 3 And P 5 The coupling reaction is carried out to generate the compound shown in the formula 7, and P 3 And P 5 View Q 2 And a targeted selection is carried out; alternatively, the group P of the compound represented by formula 3 3 And a group P of the compound represented by formula 8 5 The compounds shown in the formula 7 are respectively generated by coupling reaction with intermediate compounds, and P 3 、P 5 And intermediate compound apparent Q 2 And is selected in a targeted manner.
Further, the compound shown in the formula I-1 is prepared by a method comprising the following steps:
reacting a compound shown in a formula a-1 with a compound shown in a formula a-2 to obtain a compound shown in a formula b 1;
reacting a compound shown in a formula a-3 with a compound shown in a formula a-4 to obtain a compound shown in a formula b 2;
reacting a compound shown in a formula b1, a compound shown in a formula b2 and a compound shown in a formula a5 to obtain a compound shown in a formula b 3;
reacting a compound represented by formula b3 with a compound E to obtain a compound represented by I-1, wherein Q 1 Q and 4 is a single bond, Q 3 Independently selected from O, S, se, -CR 1 R 2 、-C＝O、-SiR 1 R 2 、-GeR 1 R 2 、-NR 1 、-BR 1 、-AlR 1 、-PR 1 、-AsR 1 、-S＝O、-SO 2 、-Se＝O、-SeO 2 、-BiR 1 ，Q 2 Is a group of formula A;
A 1 、A 2 、A 3 a is a 4 Any atom selected from halogen, and A 1 Is greater than A 2 ，A 3 Is greater than A 4 ；
In formula a5, C 1 C 2 Independently selected from-OH, -OR 1 、-SH、-SR 1 、-SeR 1 、-CHR 1 R 2 、-CR 1 O、-SiHR 1 R 2 、-GeHR 1 R 2 、-NHR 1 、-BHR 1 、-AlHR 1 、-PHR 1 、-AsHR 1 ,-SR 1 O、-SO 2 R 1 、-SeR 1 O、-SeO 2 R 1 、-BiHR 1 A substituted or unsubstituted 3 to 50 membered cyclic group;
the compound E is selected from the group consisting of A 2 、A 4 The coupling reaction is carried out to generate Q 3 A compound of (a);
the preparation method provided by the embodiment of the application can prepare the compound shown in the formula I under a more moderate condition, has higher yield, and is suitable for large-scale industrialized production.
A third aspect of an embodiment of the present application provides a functional layer comprising a compound of the foregoing first aspect. The functional layer has a layered or film-like structure, and can be used as a device of the aggregate to improve the color purity and stability of the aggregate.
According to a fourth aspect of embodiments of the present application there is provided a mixture comprising at least one compound according to the first aspect. The mixture has the advantages of narrow spectrum and high stability in the field of organic electroluminescence due to the inclusion of the compound.
The present application is not limited to the mass percentage of the compound in the mixture and the kind and mass percentage of other components, and it is within the scope of the present application as long as the compound of the first aspect of the present application is included in the mixture.
A fifth aspect of an embodiment of the present application provides an organic electroluminescent device, in which the light-emitting layer comprises the compound of the first aspect.
The organic electroluminescent device of the present application includes other functional layers common in the art in addition to the light emitting layer.
In one embodiment, the organic electroluminescent device of the present application includes a cathode layer and an anode layer, and the light emitting layer is located between the anode layer and the cathode layer.
Further, the organic electroluminescent device further comprises a hole injection layer and/or an electron injection layer, wherein the hole injection layer is positioned between the anode layer and the light emitting layer, and the electron injection layer is positioned between the cathode layer and the light emitting layer.
Still further, the organic electroluminescent layer further comprises a hole functional layer and/or an electron functional layer, wherein the hole functional layer is located between the hole injection layer and the light emitting layer, and the electron functional layer is located between the electron injection layer and the light emitting layer. The hole functional layer of the present application includes a hole transport layer and/or an electron blocking layer, and when the hole transport layer and the electron blocking layer exist at the same time, the electron blocking layer is located between the hole transport layer and the light emitting layer; the electron functional layer of the present application includes an electron transport layer and/or a hole blocking layer, and when the electron transport layer and the hole blocking layer are present at the same time, the hole blocking layer is located between the electron transport layer and the light emitting layer.
The material of each functional layer is not particularly limited, and materials commonly used in the art can be used in the present application. It will be appreciated that the thickness of each functional layer may also be consistent with the thickness of the corresponding functional layer of a device commonly known in the art.
As described above, since the light emitting layer of the organic electroluminescent device includes the aforementioned compound, the organic electroluminescent device has characteristics of excellent color purity and stability.
In one embodiment, the light emitting layer consists of the aforementioned compounds.
In another embodiment, the light emitting layer includes a host material and a dye, and the dye is the aforementioned compound.
In another embodiment, the light emitting layer includes a host material, a sensitizer, and a dye. Wherein, the compound can be used as a sensitizer to sensitize dye to emit phosphorescence, and the dye can be a phosphorescence dye commonly used in the field; alternatively, the above-mentioned compound may be sensitized as a dye to emit phosphorescence, and the sensitizer may be selected from sensitizer materials commonly used in the art.
The host material of the light-emitting layer is not particularly limited, and may be at least one of carbazole, triphenylene, benzothiophene, benzofuran, dibenzothiophene, dibenzofuran, azacarbazole, azatriphenylene, azabenzothiophene, azabenzofuran, azadibenzothiophene, and azadibenzofuran, for example.
In addition, the performance of the device can be further optimized by controlling the specific mass percent of the material in the light emitting layer.
In the practice of the present application, the mass ratio of the aforementioned compound in the light-emitting layer is generally controlled to be 0.1% or more. The doping amount of the compound in the light-emitting layer is reasonably controlled, so that the stability and the color purity of the device are further improved.
Specifically, when the light-emitting layer includes a host material and a dye, the foregoing compound is present as the dye in an amount of 0.1 to 20% by mass in the light-emitting layer, and further, the foregoing compound is present as the dye in an amount of 3 to 12% by mass in the light-emitting layer.
When the light-emitting layer comprises a main body material, a sensitizer and a dye, the mass percentage of the main body material in the light-emitting layer is 50-95%, the mass percentage of the sensitizer in the light-emitting layer is 1-30%, and the mass percentage of the dye in the light-emitting layer is 0.1-20%. Further, the mass percentage of the main material in the light-emitting layer is 70-95%, the mass percentage of the sensitizer in the light-emitting layer is 4.9-25%, and the mass percentage of the dye in the light-emitting layer is 0.1-10%
In addition, the thickness of the light-emitting layer in the electroluminescent device is not particularly limited, and is, for example, 10 to 100nm.
A sixth aspect of the embodiment of the present application further provides an electronic device, which includes the organic electroluminescent device shown in the fifth aspect. The electronic device provided by the embodiment of the application comprises a display device, and any product or component with a display function, such as a television, a digital camera, a mobile phone, a tablet personal computer, a video wall or screen, an illuminating lamp, a transmitting lamp, a wearable device, a video camera, a sign board and the like, wherein the product or component comprises the display device. The display device can be an OLED flat-panel display, an OLED vehicle-mounted display, an OLED flexible display, a full-transparent or semitransparent display, a virtual reality display or an augmented reality display and other display devices. The electronic device and the organic electroluminescent device have the same advantages as those of the prior art, and are not described herein.
Synthetic examples
Synthesis example 1: synthesis of Pt-1
1. Synthesis of intermediate 3
Raw material 1 (5.6 g,32 mmol), raw material 2 (5 g,32 mmol) and tetraphenylphosphine palladium (370 mg) were charged into a 250mL round bottom two-necked flask, and the vacuum argon was applied three times, followed by sequential injections of toluene (120 mL), ethanol (40 mL) and 2M aqueous potassium carbonate (40 mL). The reaction was carried out at 85℃for 20 hours. The reaction solution was cooled, extracted with methylene chloride and water, and the lower layer was collected and distilled off under reduced pressure to remove the solvent. The crude product was purified by column chromatography (petroleum ether/dichloromethane as eluent and the volume ratio of the two was (9:1) - (1:1)) to give 6.8g total oily colorless product 3 in 85% yield.
2. Synthesis of intermediate 5
Intermediate 3 (5 g,20 mmol), starting material 4 (1.1 g,10 mmol), potassium carbonate (8.3 g,60 mmol) and 1-methylpyrrolidone (40 mL) were charged into a 100mL round bottom flask and the vacuum and argon filling were repeated 3 times. The reaction was carried out at 170℃for 24 hours, cooled to room temperature, and the crude product was extracted with ethyl acetate and water, and the organic layer was collected. The organic layer was repeatedly washed with water 3 times, the organic layer was collected, and the organic solvent was distilled off under reduced pressure. The crude product was purified by column chromatography (petroleum ether/dichloromethane as eluent and the volume ratio of the two was (9:1) - (1:1)) to give 5.1g total oily colorless product 5 in 90% yield.
3. Synthesis of intermediate 7
Intermediate 5 (5 g,8.7 mmol), starting material 6 (1.75 g,8.7 mmol), palladium acetate (40 mg), tris (t-butylphosphorus) tetrafluoroborate (230 mg), sodium t-butoxide (5.3 g) and redistilled toluene (60 mL) were added to a 100mL round bottom flask and the vacuum and argon repeated 3 times. The reaction was carried out at 130℃for 24 hours. After cooling to room temperature, the organic layer was collected by extraction with dichloromethane and water. The organic solvent was distilled off under reduced pressure. The crude product was separated by column chromatography (petroleum ether/dichloromethane as eluent and the volume ratio of the two was (9:1) - (1:1)) to give a total of 2.3g of white product 7 in 42% yield.
4. Synthesis of Pt-1
Ligand 7 (1 g,1.6 mmol), potassium chloroplatinite (264 mg,1.6 mmol) and acetic acid (40 mL) were charged to a 100mL two-necked round bottom flask. After bubbling with argon for 30 minutes, the reaction was carried out at 135℃for 24 hours. After cooling to room temperature, the solid was collected by filtration. The crude product was separated by column chromatography (petroleum ether/dichloromethane as eluent and the volume ratio of the two was (9:1) - (1:1)) to give 868mg of orange-red product Pt-1 in 67% yield.
1 H NMR(500MHz,Chloroform-d)δ8.76(d,J＝3.0Hz,2H),7.74(d,J＝8.8Hz,2H),7.65(dd,J＝8.9,2.7Hz,2H),7.59(t,J＝8.2Hz,1H),7.52(s,1H),7.29(s,1H),7.23(d,J＝1.7Hz,2H),7.22–7.16(m,4H),7.00(t,J＝7.8Hz,2H),6.39(d,J＝8.4Hz,2H),1.36(s,18H).
FIG. 1 shows photoluminescence spectra of the compound Pt-1 of Synthesis example 1 according to the present application in methylene chloride solution. As shown in FIG. 1, the maximum luminescence wavelength of the solution of the compound is about 620 nm.
Synthesis example 2: synthesis of Pt-2
1. Synthesis of intermediate 3
Raw material 1 (5.6 g,32 mmol), raw material 2 (5.1 g,32 mmol) and tetrakis triphenylphosphine palladium (370M g) were added to a 250mL round bottom two-necked flask, and the vacuum argon was applied three times, followed by sequential injections of toluene (120 mL), ethanol (40 mL) and 2M aqueous potassium carbonate (40 mL). The reaction was carried out at 85℃for 20 hours. The reaction solution was cooled, extracted with methylene chloride and water, and the lower layer was collected and distilled off under reduced pressure to remove the solvent. The crude product was purified by column chromatography (petroleum ether/dichloromethane as eluent and the volume ratio of the two was (9:1) - (1:1)) to give 8.4g total oily colorless product 3 in 85% yield.
2. Synthesis of intermediate 5
Intermediate 3 (6.16 g,20 mmol), starting material 4 (1.1 g,10 mmol), potassium carbonate (8.3 g,60 mmol) and 1-methylpyrrolidone (40 mL) were charged into a 100mL round bottom flask and the vacuum and argon filling were repeated 3 times. The reaction was carried out at 170℃for 24 hours, cooled to room temperature, and the crude product was extracted with ethyl acetate and water, and the organic layer was collected. The organic layer was repeatedly washed with water 3 times, the organic layer was collected, and the organic solvent was distilled off under reduced pressure. The crude product was purified by column chromatography (petroleum ether/dichloromethane as eluent and the volume ratio of the two was (9:1) - (1:1)) to give 6.17g total oily colorless product 5 in 90% yield.
3. Synthesis of intermediate 7
Intermediate 5 (6 g,8.7 mmol), starting material 6 (1.75 g,8.7 mmol), palladium acetate (40 mg), tris (t-butylphosphorus) tetrafluoroborate (230 mg), sodium t-butoxide (5.3 g) and redistilled toluene (60 mL) were added to a 100mL round bottom flask and the vacuum and argon repeated 3 times. The reaction was carried out at 130℃for 24 hours. After cooling to room temperature, the organic layer was collected by extraction with dichloromethane and water. The organic solvent was distilled off under reduced pressure. The crude product was separated by column chromatography (petroleum ether/dichloromethane as eluent and the volume ratio of the two was (9:1) - (1:1)) to give a total of 2.4g of white product 7 in 38% yield.
4. Synthesis of Pt-2
Ligand 7 (1 g,1.4 mmol), potassium chloroplatinite (664 mg,1.6 mmol) and acetic acid (40 mL) were charged to a 100mL two-necked round bottom flask. After bubbling with argon for 30 minutes, the reaction was carried out at 135℃for 24 hours. After cooling to room temperature, the solid was collected by filtration. The crude product was separated by column chromatography (petroleum ether/dichloromethane as eluent and the volume ratio of the two was (9:1) - (1:1)) to give 48 mg of orange-red product Pt-2 in 33% yield.
1 H NMR(500MHz,Chloroform-d)δ8.70(d,J＝3.0Hz,2H),7.56(dd,J＝8.9,2.7Hz,2H),7.33(t,J＝8.2Hz,1H),7.30(s,1H),7.29(s,1H),7.23(d,J＝1.7Hz,2H),7.22–7.16(m,4H),7.00(t,J＝7.8Hz,2H),6.39(d,J＝8.4Hz,2H),1.36(s,18H),1.32(s,18H).
FIG. 2 shows photoluminescence spectra of the compound Pt-2 of Synthesis example 2 according to the present application in methylene chloride solution. As shown in FIG. 2, the maximum luminescence wavelength of the solution of the compound was about 625 nm.
Synthesis example 3: synthesis of Pt-3
1. Synthesis of intermediate 1
Raw material 1 (5.6 g,32 mmol), raw material 2 (5 g,32 mmol) and tetraphenylphosphine palladium (370, M g) were charged into a 250mL round bottom two-necked flask, and the vacuum was applied and argon was repeated three times, followed by sequential injections of toluene (120 mL), ethanol (40 mL) and 2M aqueous potassium carbonate (40 mL). The reaction was carried out at 85℃for 20 hours. The reaction solution was cooled, extracted with methylene chloride and water, and the lower layer was collected and distilled off under reduced pressure to remove the solvent. The crude product was purified by column chromatography (petroleum ether/dichloromethane as eluent and the volume ratio of the two was (9:1) - (1:1)) to give 6.8g total oily colorless product 3 in 85% yield.
2. Synthesis of intermediate 5
Intermediate 3 (5 g,20 mmol), starting material 4 (1.1 g,10 mmol), potassium carbonate (8.3 g,60 mmol) and 1-methylpyrrolidone (40 mL) were charged into a 100mL round bottom flask and the vacuum and argon filling were repeated 3 times. The reaction was carried out at 100℃for 24 hours and at 170℃for 24 hours, and after cooling to room temperature, the crude product was extracted with ethyl acetate and water, and the organic layer was collected. The organic layer was repeatedly washed with water 3 times, the organic layer was collected, and the organic solvent was distilled off under reduced pressure. The crude product was purified by column chromatography (petroleum ether/dichloromethane as eluent and the volume ratio of the two was (9:1) - (1:1)) to give a total of 3.4g of white product 5 in 60% yield.
3. Synthesis of intermediate 7
Intermediate 5 (5 g,8.7 mmol), starting material 6 (1.75 g,8.7 mmol), palladium acetate (40 mg), tris (t-butylphosphorus) tetrafluoroborate (230 mg), sodium t-butoxide (5.3 g) and redistilled toluene (60 mL) were added to a 100mL round bottom flask and the vacuum and argon repeated 3 times. The reaction was carried out at 135℃for 72 hours. After cooling to room temperature, toluene was removed by spin-drying under reduced pressure, and then extracted with dichloromethane and water, and the organic layer was collected. The organic solvent was distilled off under reduced pressure. The crude product was separated by column chromatography (petroleum ether/dichloromethane as eluent and the volume ratio of the two was (9:1) - (1:1)) to give a total of 2.5g of white solid 7 in 45% yield.
4. Synthesis of Pt-3
Ligand 7 (1 g,1.6 mmol), potassium chloroplatinite (730 mg,1.76 mmol) and acetic acid (40 mL) were charged to a 100mL two-necked round bottom flask. After bubbling with argon for 30 minutes, the reaction was carried out at 135℃for 24 hours. The solvent is distilled off under reduced pressure after cooling, and the crude product is washed by solvents such as dichloromethane, tetrahydrofuran, water, methanol and the like and then is filtered by suction to obtain an orange-red product Pt-3 with 520mg total and 40 percent yield.
1 H NMR(500MHz,Chloroform-d)δ8.70(d,J＝3.0Hz,2H),8.05(s,2H),7.56(dd,J＝8.9,2.7Hz,2H),7.33(t,J＝8.2Hz,1H),7.30(s,1H),7.23(d,J＝1.7Hz,2H),7.22–7.16(m,3H),7.00(t,J＝7.8Hz,2H),6.65(s,1H),1.36(s,18H),1.32(s,18H).
FIG. 3 shows photoluminescence spectra of the compound Pt-3 of Synthesis example 3 according to the present application in methylene chloride solution. As shown in FIG. 3, the maximum luminescence wavelength of the solution of the compound was about 625 nm.
Synthesis example 4: synthesis of Pt-4
1. Synthesis of intermediate 3
Reference is made to a process for the preparation of intermediate 3 of Pt-1.
2. Synthesis of intermediate 5
To a solution of raw material 4 (1.84 g,10 mmol) in Tetrahydrofuran (THF) was added sodium hydride (NaH, 0.8g,20 mmol) in portions, and after 1 hour of reaction at room temperature, intermediate 3 (5 g,20 mmol) was added, and after 24 hours of reflux reaction, the crude product was extracted with ethyl acetate and water after cooling to room temperature, and the organic layer was collected. The organic layer was repeatedly washed with water 3 times, the organic layer was collected, and the organic solvent was distilled off under reduced pressure. The crude product was purified by column chromatography (petroleum ether/dichloromethane as eluent and the volume ratio of the two was (9:1) - (1:1)) to give a total of 4.5g of white product 5 with a yield of 70%.
3. Synthesis of intermediate 7
Intermediate 5 (3.2 g,5 mmol), starting material 6 (1.02 g,5 mmol), palladium acetate (40 mg), tris (t-butylphosphorus) tetrafluoroborate (230 mg), sodium t-butoxide (5.3 g) and redistilled toluene (60 mL) were added to a 100mL round bottom flask and the vacuum was repeated 3 times with argon. The reaction was carried out at 130℃for 24 hours. After cooling to room temperature, the organic layer was collected by extraction with dichloromethane and water. The organic solvent was distilled off under reduced pressure. The crude product was separated by column chromatography (petroleum ether/dichloromethane as eluent and the volume ratio of the two was (9:1) - (1:1)) to give a total of 1.2g of white product 7 in 35% yield.
4. Synthesis of Pt-4
Ligand 7 (1 g,1.45 mmol), potassium chloroplatinite (602 mg,1.45 mmol) and acetic acid (40 mL) were charged to a 100mL two-necked round bottom flask. After bubbling with argon for 30 minutes, the reaction was carried out at 135℃for 24 hours. After cooling to room temperature, the solid was collected by filtration. The crude product was separated by column chromatography (petroleum ether/dichloromethane as eluent and the volume ratio of the two was (9:1) - (1:1)) to give 834mg of red product Pt-4 in 65% yield.
1 H NMR(500MHz,DMSO-d6)δ8.76(s,2H),8.47(s,2H),8.12(s,2H),7.68–7.66(m,3H),7.56(s,1H),7.43(s,2H),7.05(s,2H),6.95(t,J＝7.5Hz,2H),6.10(d,J＝7.5Hz,2H),5.32(t,J＝1.0Hz,1H),2.46(s,6H),1.32(s,18H).
FIG. 4 shows photoluminescence spectra of the compound Pt-4 of Synthesis example 4 according to the present application in methylene chloride solution. As shown in FIG. 4, the maximum luminescence wavelength of the solution of the compound was about 670 nm.
Synthesis example 5: synthesis of Pt-5
1. Synthesis of intermediate 5:
reference is made to a process for the preparation of intermediate 5 of Pt-4.
2. Synthesis of intermediate 7
5 (6.48 g,10 mmol) was added to PEG400 system containing NaOH (1.6 g,40 mmol) and reacted at 170℃for 24 hours. After cooling to room temperature, water was added and the solid was collected by filtration and dried. The resulting solid was dissolved in Tetrahydrofuran (THF), sodium hydride (NaH, 0.8g,20 mmol) was added in portions, and after reflux reaction for 1 hour, cooled to room temperature, methyl iodide (5 g,20 mmol) was added, reflux reaction was carried out for 24 hours, after cooling to room temperature, the crude product was extracted with ethyl acetate and water, and the organic layer was collected. The organic layer was repeatedly washed with water 3 times, the organic layer was collected, and the organic solvent was distilled off under reduced pressure. The crude product was purified by column chromatography (petroleum ether/dichloromethane as eluent and the volume ratio of the two was (9:1) - (1:1)) to give a total of 1.75g of white product 7 in 28% yield.
3. Synthesis of intermediate 8
Intermediate 7 (1.56 g,2.5 mmol), starting material 6 (0.5 g,2.5 mmol), palladium acetate (40 mg), tris (t-butylphosphorus) tetrafluoroborate (230 mg), sodium t-butoxide (5.3 g) and redistilled toluene (60 mL) were added to a 100mL round bottom flask and the vacuum was evacuated and argon repeated 3 times. The reaction was carried out at 130℃for 24 hours. After cooling to room temperature, the organic layer was collected by extraction with dichloromethane and water. The organic solvent was distilled off under reduced pressure. The crude product was separated by column chromatography (petroleum ether/dichloromethane as eluent and the volume ratio of the two was (9:1) - (1:1)) to give a total of 0.55g of white product 8 in 33% yield.
4. Synthesis of intermediate Pt-5
Ligand 8 (0.5 g,0.75 mmol), potassium chloroplatinite (310 mg,0.75 mmol) and acetic acid (40 mL) were charged to a 100mL two-necked round bottom flask. After bubbling with argon for 30 minutes, the reaction was carried out at 135℃for 24 hours. After cooling to room temperature, the solid was collected by filtration. The crude product was separated by column chromatography (petroleum ether/dichloromethane as eluent and the volume ratio of the two was (9:1) - (1:1)) to give a total of 402mg of red product Pt-5 in 62% yield.
1 H NMR(500MHz,DMSO-d6)δ8.66(s,2H),8.37(s,2H),8.02(s,2H),7.58–7.56(m,3H),7.50(s,1H),7.32(s,2H),7.15(s,2H),6.90(t,J＝7.5Hz,2H),6.15(d,J＝7.5Hz,2H),5.36(t,J＝1.0Hz,1H),1.76(s,12H),1.33(s,18H).
The various chemicals in the above synthesis examples are all commercially available.
Hereinafter, an organic electroluminescent device including the organic compound according to the present invention will be described in more detail by means of device examples.
Device example 1
The organic electroluminescent device of this embodiment is of a double-main structure, and the dye is Pt-1 of synthetic embodiment 1, and the device structure is:
ITO/HATCN(5nm)/TAPC(30nm)/TCTA(10nm)/mCBP(5nm)/TAPC:POT2T:Pt-1(48.5％:48.5％:3％,20nm)/POT2T(10nm)/TPBi(30nm)/Liq(2nm)/Al(100nm)
device example 2
The organic electroluminescent device of this embodiment is of a double-main structure, and the dye is Pt-1 of synthetic embodiment 1, and the device structure is:
ITO/HATCN(5nm)/TAPC(30nm)/TCTA(10nm)/mCBP(5nm)/TAPC:POT2T:Pt-1(47％:47％:6％,20nm)/POT2T(10nm)/TPBi(30nm)/Liq(2nm)/Al(100nm)
device example 3
The organic electroluminescent device of this embodiment is of a double-main structure, and the dye is Pt-1 of synthetic embodiment 1, and the device structure is:
ITO/HATCN(5nm)/TAPC(30nm)/TCTA(10nm)/mCBP(5nm)/TAPC:POT2T:Pt-1(44％:44％:12％,20nm)/POT2T(10nm)/TPBi(30nm)/Liq(2nm)/Al(100nm)
device example 4
The organic electroluminescent device of this embodiment is of a double-main structure, and the dye is Pt-2 of synthetic embodiment 2, the device structure is:
ITO/HATCN(5nm)/TAPC(30nm)/TCTA(10nm)/mCBP(5nm)/TAPC:POT2T:Pt-2(48.5％:48.5％:3％,20nm)/POT2T(10nm)/TPBi(30nm)/Liq(2nm)/Al(100nm)
Device example 5
The organic electroluminescent device of this embodiment is of a double-main structure, and the dye is Pt-3 of synthetic embodiment 3, the device structure is:
ITO/HATCN(5nm)/TAPC(30nm)/TCTA(10nm)/mCBP(5nm)/TAPC:POT2T:Pt-3(48.5％:48.5％:3％,20nm)/POT2T(10nm)/TPBi(30nm)/Liq(2nm)/Al(100nm)
device example 6
The organic electroluminescent device of this embodiment is of a double-main structure, and the dye is Pt-4 of synthetic embodiment 4, the device structure is:
ITO/HATCN(5nm)/TAPC(30nm)/TCTA(10nm)/mCBP(5nm)/TAPC:POT2T:Pt-4(48.5％:48.5％:3％,20nm)/POT2T(10nm)/TPBi(30nm)/Liq(2nm)/Al(100nm)
comparative example 1-comparative example 2
The device structure of comparative examples 1-2 was substantially identical to that of example 1, except that the dye of example 1 was replaced with another dye.
Wherein the dye of comparative example 1 is D1 and the dye of comparative example 2 is D2.
The electroluminescence spectra of the devices of the examples and the comparative examples are characterized, and parameters such as the maximum emission wavelength λmax of the devices are shown in table 1. Fig. 5 is an electroluminescence spectrum of the organic electroluminescent device of device example 1, and fig. 6 is an external quantum efficiency-luminance curve of the organic electroluminescent device of device example 1. As shown in fig. 5, the maximum wavelength of electroluminescence of device example 1 was 620nm. As shown in fig. 6, the external quantum efficiency of device example 1 decreases slowly with an increase in luminance, i.e., device example 1 has the advantage of a decrease in efficiency roll.
TABLE 1
"-" indicates no measurement.
As can be seen from table 1: compared with the comparative example, the technical scheme provided by the application is that when the organic light-emitting layer comprises the compound shown in the formula I, the organic electroluminescent device not only has narrower half-peak width but also has better color purity, and meanwhile, the efficiency roll is reduced under high brightness to have excellent stability.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the embodiments of the present application, and are not limited thereto; although embodiments of the present application have been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application.
Claims (20)
1. A compound characterized in that the compound has a structure represented by formula 1,
in the formula I, M represents Pd (II) or Pt (II);
Z 1 、Z 2 、Z 3 z is as follows 4 Independently selected from single bond, O, S or Se;
X 1 、X 2 、X 3 x is as follows 4 Any two of them are N, and the other two are C;
Q 1 、Q 2 、Q 3 q and 4 independently selected from single bond, O, S, se, -CR 1 R 2 、-C＝O、-SiR 1 R 2 、-GeR 1 R 2 、-NR 1 、-BR 1 、-AlR 1 、-PR 1 、-AsR 1 、-S＝O、-SO 2 、-Se＝O、-SeO 2 、-BiR 1 Or a group of formula a, and Q 1 、Q 2 、Q 3 Q and 4 at least one of them is a group of the formula A, in which L n Selected from L 5 、L 6 、L 7 L and 8 ，Y n 、Y m independently selected from Y 1 、Y 2 、Y 3 、Y 4 、Y 5 、Y 6 、Y 7 Y is as follows 8 One of them;
L 1 、L 2 、L 3 、L 4 、L 5 、L 6 、L 7 l and 8 independently selected from substituted or unsubstituted 3 to 50 membered cyclic groups;
Y 1 、Y 2 、Y 3 、Y 4 、Y 5 、Y 6 、Y 7 y is as follows 8 Independently selected from O, S, se, -CR 1 R 2 、-C＝O、-SiR 1 R 2 、-GeR 1 R 2 、-NR 1 、-BR 1 、-AlR 1 、-PR 1 、-AsR 1 ,-S＝O、-SO 2 、-Se＝O、-SeO 2 、-BiR 1 A substituted or unsubstituted 3-to 50-membered cyclic group and Y n 、Y m Not both benzene rings;
wherein R is 1 、R 2 Independently selected from hydrogen, deuterium, halogen, hydroxy, thiol, nitro, cyano, isocyano, sulfone, hydroxylamine, carboxyl, carbonyl, or one of the following substituted or unsubstituted groups: C6-C48 monocyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbon, C3-C48 monocyclic heteroaromatic hydrocarbon or polycyclic heteroaromatic hydrocarbon, C1-C36 alkyl, C2-C36 heterocycloalkyl, C2-C36 alkenyl, C2-C36 alkynyl, amino, C1-C36 alkoxy, C1-C36 alkylthio, amido, silicon base and boron base.
2. The compound of claim 1, wherein the compound has a structure of formula II or formula III,
in the formula II, X 11 X is as follows 12 Is L 1 Is a ring-forming atom, X 21 、X 22 X is as follows 23 Is L 2 Is a ring-forming atom, X 31 、X 32 X is as follows 33 Is L 3 Is a ring-forming atom, X 41 X is as follows 42 Is L 4 Ring-forming atoms of Q 1 、Q 3 Q and 4 independently selected from single bond, O, S, se, -CR 1 R 2 、-C＝O、-SiR 1 R 2 、-GeR 1 R 2 、-NR 1 、-BR 1 、-AlR 1 、-PR 1 、-AsR 1 、-S＝O、-SO 2 、-Se＝O、-SeO 2 、-BiR 1 ；
In the formula III, X 11 、X 12 X is as follows 13 Is L 1 Is a ring-forming atom, X 21 、X 22 X is as follows 23 Is L 2 Is a ring-forming atom, X 31 、X 32 X is as follows 33 Is L 3 Is a ring-forming atom, X 41 、X 42 X is as follows 43 Is L 4 Ring-forming atoms of Q 1 Q and 4 independently selected from single bond, O, S, se, -CR 1 R 2 、-C＝O、-SiR 1 R 2 、-GeR 1 R 2 、-NR 1 、-BR 1 、-AlR 1 、-PR 1 、-AsR 1 、-S＝O、-SO 2 、-Se＝O、-SeO 2 、-BiR 1 。
3. A compound according to claim 1 or 2, wherein the compound has a structure represented by any one of M1 to M40,
Wherein Ar is 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 Each independently selected from substituted or unsubstituted 5-8 membered cyclic groups, R 3 、R 4 、R 5 、R 6 、R 7 、R 8 Independently selected from hydrogen, deuterium, halogen, hydroxy, thiol, nitro, cyano, isocyano, sulfone, hydroxylamine, carboxyl, carbonyl, or one of the following substituted or unsubstituted groups: C6-C48 monocyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbon, C3-C48 monocyclic heteroaromatic hydrocarbon or polycyclic heteroaromatic hydrocarbon, C1-C36 alkyl, C2-C36 heterocycloalkyl, C2-C36 alkenyl, C2-C36 alkynyl, amino, C1-C36 alkoxy, C1-C36 alkylthio, amido, silicon base and boron base.
4. A compound according to claim 3, wherein the compound has a structure represented by any one of P1 to P200, S1 to S200, T1 to T200, E1 to E200, F1 to F200, K1 to K200, G1 to G200, R1 to R200 and X1 to X8,
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5. a compound according to any one of claims 1 to 4, wherein the compound is obtainable by a process comprising reacting a compound of formula I-1 with a halide of a metal M,
in the formula I-1, G 1 ～G 4 Each independently selected from hydroxy, alkoxy, mercapto, alkylthio, selenohydroxy, alkylseleno, or absent.
6. The compound of claim 5, wherein the compound of formula I-1 is prepared by a process comprising:
Or alternatively, the process may be performed,
wherein P is 1 、P 2 、P 3 、P 4 、P 5 、P 6 、P 7 、P 8 Each independently selected from groups for which a coupling reaction occurs.
7. The compound of claim 6, wherein the compound of formula I-1 is prepared by a process comprising:
reacting a compound shown in a formula a-1 with a compound shown in a formula a-2 to obtain a compound shown in a formula b 1;
reacting a compound shown in a formula a-3 with a compound shown in a formula a-4 to obtain a compound shown in a formula b 2;
reacting a compound shown in a formula b1, a compound shown in a formula b2 and a compound shown in a formula a5 to obtain a compound shown in a formula b 3;
reacting a compound represented by the formula b3 with a compound E to obtain a compound represented by I-1, wherein,Q 1 q and 4 is a single bond, Q 3 Independently selected from O, S, se, -CR 1 R 2 、-C＝O、-SiR 1 R 2 、-GeR 1 R 2 、-NR 1 、-BR 1 、-AlR 1 、-PR 1 、-AsR 1 、-S＝O、-SO 2 、-Se＝O、-SeO 2 、-BiR 1 ，Q 2 Is a group of formula A;
A 1 、A 2 、A 3 a is a 4 Any atom selected from halogen, and A 1 Is greater than A 2 ，A 3 Is greater than A 4 ；
In formula a5, C 1 C 2 Independently selected from-OH, -OR 1 、-SH、-SR 1 、-SeR 1 、-CHR 1 R 2 、-CR 1 O、-SiHR 1 R 2 、-GeHR 1 R 2 、-NHR 1 、-BHR 1 、-AlHR 1 、-PHR 1 、-AsHR 1 ,-SR 1 O、-SO 2 R 1 、-SeR 1 O、-SeO 2 R 1 、-BiHR 1 A substituted or unsubstituted 3 to 50 membered cyclic group;
the compound E is selected from the group consisting of A 2 、A 4 The coupling reaction is carried out to generate Q 3 A compound of (a);
8. a process for the preparation of a compound according to any one of claims 1 to 7, comprising the steps of:
The compound shown in the formula I-1 is obtained by reacting with a halogenide of metal M,
in the formula I-1, the components are as follows,G 1 ～G 4 each independently selected from hydroxy, alkoxy, mercapto, alkylthio, selenohydroxy, alkylseleno, or absent.
9. The preparation method according to claim 8, wherein the compound represented by formula I-1 is prepared by a method comprising the following processes:
or alternatively, the process may be performed,
wherein P is 1 、P 2 、P 3 、P 4 、P 5 、P 6 、P 7 、P 8 Each independently selected from groups for which a coupling reaction occurs.
10. The preparation method according to claim 9, wherein the compound represented by formula I-1 is prepared by a method comprising the following processes:
reacting a compound shown in a formula a-1 with a compound shown in a formula a-2 to obtain a compound shown in a formula b 1;
reacting a compound shown in a formula a-3 with a compound shown in a formula a-4 to obtain a compound shown in a formula b 2;
reacting a compound shown in a formula b1, a compound shown in a formula b2 and a compound shown in a formula a5 to obtain a compound shown in a formula b 3;
reacting a compound represented by formula b3 with a compound E to obtain a compound represented by I-1, wherein Q 1 Q and 4 is a single bond, Q 3 Independently selected from O, S, se, -CR 1 R 2 、-C＝O、-SiR 1 R 2 、-GeR 1 R 2 、-NR 1 、-BR 1 、-AlR 1 、-PR 1 、-AsR 1 、-S＝O、-SO 2 、-Se＝O、-SeO 2 、-BiR 1 ，Q 2 Is a group of formula A;
A 1 、A 2 、A 3 A is a 4 Any atom selected from halogen, and A 1 Is greater than A 2 ，A 3 Is greater than A 4 ；
In formula a5, C 1 C 2 Independently selected from-OH, -OR 1 、-SH、-SR 1 、-SeR 1 、-CHR 1 R 2 、-CR 1 O、-SiHR 1 R 2 、-GeHR 1 R 2 、-NHR 1 、-BHR 1 、-AlHR 1 、-PHR 1 、-AsHR 1 ,-SR 1 O、-SO 2 R 1 、-SeR 1 O、-SeO 2 R 1 、-BiHR 1 A substituted or unsubstituted 3 to 50 membered cyclic group;
the compound E is selected from the group consisting of A 2 、A 4 The coupling reaction is carried out to generate Q 3 A compound of (a);
11. a functional layer comprising a compound according to any one of claims 1 to 7 or a compound prepared by the preparation method according to any one of claims 8 to 10.
12. A mixture comprising at least one compound according to any one of claims 1 to 7 or a compound prepared by a method according to any one of claims 8 to 10.
13. An organic electroluminescent device comprising a light-emitting layer comprising the compound according to any one of claims 1 to 7 or the compound produced by the production method according to any one of claims 8 to 10.
14. The organic electroluminescent device of claim 13, wherein the light-emitting layer consists of the compound.
15. The organic electroluminescent device of claim 13, wherein the light-emitting layer comprises a host material and a dye, the dye being the compound.
16. The organic electroluminescent device according to claim 13, wherein the light-emitting layer comprises a host material, a sensitizer, and a dye, and one of the sensitizer and the dye is the compound.
17. The organic electroluminescent device according to claim 15, wherein the mass percentage of the dye in the light-emitting layer is 0.1 to 20%.
18. The organic electroluminescent device according to claim 16, wherein the mass percentage of the host material in the light-emitting layer is 50-95%, the mass percentage of the sensitizer in the light-emitting layer is 1-30%, and the mass percentage of the dye in the light-emitting layer is 0.1-20%.
19. The organic electroluminescent device of any one of claims 15-18, wherein the host material is selected from at least one of carbazole, triphenylene, benzothiophene, benzofuran, dibenzothiophene, dibenzofuran, azacarbazole, azatriphenylene, azabenzothiophene, azabenzofuran, azadibenzothiophene, azadibenzofuran.
20. An electronic device, characterized in that it comprises an organic electroluminescent device as claimed in any one of claims 13-19.
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