CN115894558A - Aromatic phosphine oxide compound containing diphenylfluorene and preparation method thereof - Google Patents
Aromatic phosphine oxide compound containing diphenylfluorene and preparation method thereof Download PDFInfo
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- CN115894558A CN115894558A CN202210952156.4A CN202210952156A CN115894558A CN 115894558 A CN115894558 A CN 115894558A CN 202210952156 A CN202210952156 A CN 202210952156A CN 115894558 A CN115894558 A CN 115894558A
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- CN
- China
- Prior art keywords
- reaction
- fluorene
- bis
- compound
- diphenylfluorene
- Prior art date
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- -1 Aromatic phosphine oxide compound Chemical class 0.000 title claims abstract description 78
- QTPLEVOKSWEYAC-UHFFFAOYSA-N 1,2-diphenyl-9h-fluorene Chemical compound C=1C=CC=CC=1C1=C2CC3=CC=CC=C3C2=CC=C1C1=CC=CC=C1 QTPLEVOKSWEYAC-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims description 10
- 239000000463 material Substances 0.000 claims abstract description 37
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims description 49
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 37
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 24
- 238000002347 injection Methods 0.000 claims description 22
- 239000007924 injection Substances 0.000 claims description 22
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 18
- 239000013067 intermediate product Substances 0.000 claims description 17
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 15
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- 230000005525 hole transport Effects 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000007810 chemical reaction solvent Substances 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000005859 coupling reaction Methods 0.000 claims description 9
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 150000002941 palladium compounds Chemical class 0.000 claims description 8
- 239000007800 oxidant agent Substances 0.000 claims description 7
- VQTLUEKUYMRVDS-UHFFFAOYSA-N 9,9-bis(4-bromophenyl)fluorene Chemical compound C1=CC(Br)=CC=C1C1(C=2C=CC(Br)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 VQTLUEKUYMRVDS-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 4
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- AHDSYMVAUJZCOP-UHFFFAOYSA-N 9-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]carbazole Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C(N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AHDSYMVAUJZCOP-UHFFFAOYSA-N 0.000 claims description 3
- 230000000903 blocking effect Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- HYBLFOADKYTPGT-UHFFFAOYSA-N 9,9-bis(4-chlorophenyl)fluorene Chemical group C1=CC(Cl)=CC=C1C1(C=2C=CC(Cl)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 HYBLFOADKYTPGT-UHFFFAOYSA-N 0.000 claims description 2
- JMGIDYACTFKFLK-UHFFFAOYSA-N 9,9-bis(4-iodophenyl)fluorene Chemical compound C1=CC(I)=CC=C1C1(C=2C=CC(I)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 JMGIDYACTFKFLK-UHFFFAOYSA-N 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- CCZVEWRRAVASGL-UHFFFAOYSA-N lithium;2-methanidylpropane Chemical compound [Li+].CC(C)[CH2-] CCZVEWRRAVASGL-UHFFFAOYSA-N 0.000 claims description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 230000003111 delayed effect Effects 0.000 abstract description 13
- 230000005284 excitation Effects 0.000 abstract description 10
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 238000013461 design Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 108091006149 Electron carriers Proteins 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 33
- 239000002904 solvent Substances 0.000 description 26
- 239000012074 organic phase Substances 0.000 description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 239000012043 crude product Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 238000001704 evaporation Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 8
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 8
- 239000003208 petroleum Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 238000004440 column chromatography Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 230000005526 G1 to G0 transition Effects 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000002189 fluorescence spectrum Methods 0.000 description 6
- 238000002411 thermogravimetry Methods 0.000 description 6
- 238000002211 ultraviolet spectrum Methods 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- 238000001819 mass spectrum Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- SWJDUPQQVCCPEH-UHFFFAOYSA-N 9-(4-bromophenyl)-9h-fluorene Chemical compound C1=CC(Br)=CC=C1C1C2=CC=CC=C2C2=CC=CC=C21 SWJDUPQQVCCPEH-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910015711 MoOx Inorganic materials 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 4
- 238000001194 electroluminescence spectrum Methods 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 4
- ATTVYRDSOVWELU-UHFFFAOYSA-N 1-diphenylphosphoryl-2-(2-diphenylphosphorylphenoxy)benzene Chemical compound C=1C=CC=CC=1P(C=1C(=CC=CC=1)OC=1C(=CC=CC=1)P(=O)(C=1C=CC=CC=1)C=1C=CC=CC=1)(=O)C1=CC=CC=C1 ATTVYRDSOVWELU-UHFFFAOYSA-N 0.000 description 3
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000007707 calorimetry Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- ZVFQEOPUXVPSLB-UHFFFAOYSA-N 3-(4-tert-butylphenyl)-4-phenyl-5-(4-phenylphenyl)-1,2,4-triazole Chemical compound C1=CC(C(C)(C)C)=CC=C1C(N1C=2C=CC=CC=2)=NN=C1C1=CC=C(C=2C=CC=CC=2)C=C1 ZVFQEOPUXVPSLB-UHFFFAOYSA-N 0.000 description 2
- KRSVCSUXXKTMTN-UHFFFAOYSA-N BrC1=CC=C(C=C1)C1(C2=CC=CC=C2C=2C=CC=CC1=2)C1=CC=C(C=C1)N1C2=CC=CC=C2C=2C=CC=CC1=2 Chemical compound BrC1=CC=C(C=C1)C1(C2=CC=CC=C2C=2C=CC=CC1=2)C1=CC=C(C=C1)N1C2=CC=CC=C2C=2C=CC=CC1=2 KRSVCSUXXKTMTN-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- BHIIGRBMZRSDRI-UHFFFAOYSA-N [chloro(phenoxy)phosphoryl]oxybenzene Chemical compound C=1C=CC=CC=1OP(=O)(Cl)OC1=CC=CC=C1 BHIIGRBMZRSDRI-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical group C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 2
- 229960001701 chloroform Drugs 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 229940045803 cuprous chloride Drugs 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- XNKVIGSNRYAOQZ-UHFFFAOYSA-N dibenzofluorene Chemical compound C12=CC=CC=C2C2=CC=CC=C2C2=C1CC1=CC=CC=C12 XNKVIGSNRYAOQZ-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- VGGNVBNNVSIGKG-UHFFFAOYSA-N n,n,2-trimethylaziridine-1-carboxamide Chemical compound CC1CN1C(=O)N(C)C VGGNVBNNVSIGKG-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- LZJHACNNMBYMSO-UHFFFAOYSA-N 1,1-dimethyl-3-propylurea Chemical compound CCCNC(=O)N(C)C LZJHACNNMBYMSO-UHFFFAOYSA-N 0.000 description 1
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 1
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 description 1
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 description 1
- KZDXETFJSVYULZ-UHFFFAOYSA-N 9-[4-[9-(4-diphenylphosphorylphenyl)fluoren-9-yl]phenyl]carbazole Chemical compound C1(=CC=CC=C1)P(=O)(C1=CC=CC=C1)C1=CC=C(C=C1)C1(C2=CC=CC=C2C=2C=CC=CC1=2)C1=CC=C(C=C1)N1C2=CC=CC=C2C=2C=CC=CC1=2 KZDXETFJSVYULZ-UHFFFAOYSA-N 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- IBTCZUXKFPQNMB-UHFFFAOYSA-N [B].OC=1C=CC=C2C=CC=NC12.OC=1C=CC=C2C=CC=NC12.OC=1C=CC=C2C=CC=NC12.OC=1C=CC=C2C=CC=NC12.[Li] Chemical group [B].OC=1C=CC=C2C=CC=NC12.OC=1C=CC=C2C=CC=NC12.OC=1C=CC=C2C=CC=NC12.OC=1C=CC=C2C=CC=NC12.[Li] IBTCZUXKFPQNMB-UHFFFAOYSA-N 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 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
- 150000001408 amides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- RZSMSXXOYMFIKN-UHFFFAOYSA-N bromo(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(Br)C1=CC=CC=C1 RZSMSXXOYMFIKN-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
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- 238000010276 construction Methods 0.000 description 1
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 1
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- 238000010168 coupling process Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
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- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
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- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- ZTLUNQYQSIQSFK-UHFFFAOYSA-N n-[4-(4-aminophenyl)phenyl]naphthalen-1-amine Chemical compound C1=CC(N)=CC=C1C(C=C1)=CC=C1NC1=CC=CC2=CC=CC=C12 ZTLUNQYQSIQSFK-UHFFFAOYSA-N 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- YNUJADNRNHJXDT-UHFFFAOYSA-N palladium;pentane-2,4-dione Chemical compound [Pd].CC(=O)CC(C)=O.CC(=O)CC(C)=O YNUJADNRNHJXDT-UHFFFAOYSA-N 0.000 description 1
- QJPQVXSHYBGQGM-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 QJPQVXSHYBGQGM-UHFFFAOYSA-N 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical group O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 description 1
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- 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
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- Electroluminescent Light Sources (AREA)
Abstract
The invention provides an aromatic phosphine oxide compound containing diphenylfluorene as well as a synthesis method and application thereof. The compound serving as a thermal excitation delayed fluorescent material can ensure effective transfer of energy, realize simultaneous transmission of holes and electron carriers, is beneficial to design and performance improvement of devices, can be used for preparing an ultra-low voltage driven efficient thermal excitation delayed near ultraviolet light-emitting device, has good thermodynamic stability, and improves the light-emitting efficiency and brightness of the organic electroluminescent material.
Description
Technical Field
The invention belongs to the technical field of electroluminescent materials, and particularly relates to an aromatic phosphine oxide compound based on diphenylfluorene and application thereof as a thermal excitation delayed fluorescence material to preparation of an electroluminescent device.
Background
Organic Light Emitting Diodes (OLEDs) are of great significance in solid-state lighting and full-color display, where the efficiency and brightness of yellow and green devices are a great breakthrough, while the low efficiency and brightness of blue devices are on the standby, so that the construction of efficient blue devices is of certain research significance.
Organic molecules with Thermally Activated Delayed Fluorescence (TADF) properties are typically donor-acceptor type molecules and have small triplet and singlet energies that are very poor. The small singlet state and triplet state energy range difference can convert triplet state electrons into singlet state electrons, thereby improving the utilization rate of electrons and realizing 100% internal quantum efficiency. However, at high concentration, an electron annihilation phenomenon occurs, and the efficiency is lowered. Phosphorescent materials prior to TADF have also met with great success. The organometallic phosphor containing a noble metal has an emission triplet state due to efficient spin orbit coupling, and can achieve higher External Quantum Efficiency (EQE). Although highly efficient blue phosphorescent organic light emitting diodes are reported, they are not popular due to the need to use expensive and non-renewable precious metals.
In previous studies, wong et al prepared three spirofluorene near-uv emitting molecules (k.t.wong, adv.mater, 2005,17,992-996.). Photoluminescence shows double emission of 370 nm and 390nm, a non-doped device realizes near ultraviolet electroluminescence and has good luminous performance, but the efficiency roll-off of the device is quite serious due to phenomena such as exciton quenching and the like caused by unbalanced carrier transmission and the like.
Therefore, organic thermal excitation delayed fluorescence aromatic phosphine oxide materials are further researched, so that the electroluminescent device has good electron transmission capacity, good external quantum efficiency and efficiency stability, good electroluminescent comprehensive performance is obtained, and the practical use requirements are met.
Disclosure of Invention
In order to solve the problems, the invention provides a thermal excitation delayed fluorescence aromatic phosphine oxide compound containing diphenylfluorene, which has reasonable molecular design, can improve the electron transport capability of the material by introducing phosphine oxide, and can be used as a light-emitting layer object material to prepare an ultra-low voltage driven and high-efficiency thermal excitation delayed fluorescence blue light device, thereby completing the invention.
It is an object of the first aspect of the present invention to provide a diphenylfluorene-containing aromatic phosphine oxide compound having the following structure:
wherein X is selected from substituted or unsubstituted carbazolyl or nitrogenated phenyl.
The second aspect of the invention aims to provide a preparation method of the aromatic phosphine oxide compound containing the diphenylfluorene, which comprises the steps of taking 9,9-bis (4-halogenated phenyl) -9H-fluorene as a raw material, firstly carrying out coupling reaction with a nitrogen-containing aromatic compound, then carrying out nucleophilic substitution with diphenyl phosphorus halide, and oxidizing to obtain the aromatic phosphine oxide compound containing the diphenylfluorene.
The method specifically comprises the following steps:
and 3, adding the intermediate product II into a reaction solvent III, adding an oxidant, stirring for reaction, and performing post-treatment to obtain the aromatic phosphine oxide compound containing the diphenylfluorene.
The third aspect of the present invention is to provide an electroluminescent device, wherein the material of the luminescent layer of the electroluminescent device comprises one or more of the dibenzofluorene-containing aromatic phosphine oxide compounds described in claim 1;
the electroluminescent device comprises a conductive anode layer, a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode conductive layer.
The aromatic phosphine oxide compound containing the diphenylfluorene provided by the invention has the following beneficial effects:
(1) The aromatic phosphine oxide compound containing the diphenylfluorene has good luminescence performance, the electroluminescent peak position is 350-405nm, and the aromatic phosphine oxide compound is an organic blue light guest material with high luminescent color purity, and the performance of the blue light guest material is further improved.
(2) The aromatic phosphine oxide compound containing the diphenylfluorene has good thermal stability, so that the prepared electroluminescent device has stable performance.
(3) The diphenyl fluorene-containing thermally-excited delayed fluorescence aromatic phosphine oxide compound provided by the invention utilizes the electron donor to improve the electron transport performance of the material, and can be used for preparing an ultra-low voltage driven high-efficiency thermally-excited delayed fluorescence blue light device.
(4) The external quantum efficiency of the electroluminescent device prepared by taking the aromatic phosphine oxide compound containing the diphenylfluorene as a luminescent layer material is improved, and the current efficiency and the power efficiency are effectively improved.
Drawings
FIG. 1 shows a UV spectrum and a fluorescence spectrum of compound I in example 1 of the present invention;
FIG. 2 shows a UV spectrum and a fluorescence spectrum of compound II in example 2 of the present invention;
FIG. 3 shows a UV spectrum and a fluorescence spectrum of compound III in example 3 of the present invention;
FIG. 4 is a graph showing the voltage-luminance relationship of an electro-blue light device in example 1 of the present invention;
FIG. 5 is a graph showing the luminance-current efficiency relationship of an electro-blue light device in example 1 of the present invention;
FIG. 6 shows the luminance-power efficiency relationship of an electro-blue light device in example 1 of the present invention;
FIG. 7 shows the luminance-external quantum efficiency curve efficiency of an electroblue device in example 1 of the present invention;
FIG. 8 is a graph showing an electroluminescence spectrum of a blue electroluminescent device in example 1 of the present invention;
FIG. 9 is a graph showing the voltage-luminance relationship of an electro-blue light device in example 2 of the present invention;
FIG. 10 is a graph showing the luminance-current efficiency relationship of an electro-blue light device in example 2 of the present invention;
FIG. 11 is a graph showing the luminance-power efficiency relationship of an electro-blue light device in example 2 of the present invention;
FIG. 12 shows the current density-external quantum efficiency curve efficiency of the blue electroluminescent device in example 2 of the present invention;
FIG. 13 is a graph showing an electroluminescence spectrum of a blue electroluminescent device in example 2 of the present invention;
FIG. 14 is a graph showing the voltage-luminance relationship of an electro-blue light device in example 3 of the present invention;
FIG. 15 is a graph showing the luminance-current efficiency relationship of an electro-blue light device in example 3 of the present invention;
FIG. 16 shows the luminance-power efficiency relationship of an electro-blue light device in example 3 of the present invention;
FIG. 17 shows the luminance-external quantum efficiency curve efficiency of an electroblue device in example 3 of the present invention;
FIG. 18 is a graph showing an electroluminescence spectrum of a blue electroluminescent device in example 3 of the present invention;
FIG. 19 shows a thermogravimetric analysis of compound I in example 1 of the present invention;
FIG. 20 shows a thermogravimetric analysis chart of compound II in example 2 of the present invention;
FIG. 21 shows a thermogravimetric analysis of compound III in example 3 of the present invention.
Detailed Description
The present invention will now be described in detail by way of specific embodiments, and features and advantages of the present invention will become more apparent and apparent from the following description.
The invention provides an aromatic phosphine oxide compound containing diphenylfluorene, which takes diphenylfluorene as a matrix, is connected with an aromatic nitrogen-containing group and an aromatic phosphine oxide group through molecular design, and can be used as a thermal excitation delayed fluorescent material to ensure the effective transfer of energy, realize the simultaneous transmission of a cavity and an electron carrier, be beneficial to the design and the improvement of performance of a device, be capable of preparing an ultra-low voltage driven high-efficiency thermal excitation delayed near ultraviolet light-emitting device, have good thermodynamic stability, and improve the luminous efficiency and the brightness of an organic electroluminescent material.
The invention provides an aromatic phosphine oxide compound containing diphenylfluorene, which has the following structure:
wherein X is selected from substituted or unsubstituted carbazolyl or nitrogenous phenyl, preferably diphenylamine-phenyl, N-carbazolyl or N-carbazolylphenyl.
Preferably, the dibenzofluorene-containing aromatic phosphine oxide compound is selected from one of the following compounds:
the aromatic phosphine oxide compound containing the diphenylfluorene provided by the invention can be used as a thermal excitation delayed fluorescence material for preparing an electroluminescent device.
The invention also provides a preparation method of the aromatic phosphine oxide compound containing the diphenylfluorene, which comprises the steps of taking 9,9-bi (4-halogenated phenyl) -9H-fluorene as a raw material, performing coupling reaction with a nitrogen-containing aromatic compound, performing nucleophilic substitution with diphenyl phosphorus halide, and oxidizing to obtain the aromatic phosphine oxide compound containing the diphenylfluorene.
The 9,9-bis (4-halophenyl) -9H-fluorene is selected from 9,9-bis (4-chlorophenyl) -9H-fluorene, 9,9-bis (4-bromophenyl) -9H-fluorene or 9,9-bis (4-iodophenyl) -9H-fluorene, preferably 9,9-bis (4-bromophenyl) -9H-fluorene.
The nitrogen-containing aromatic compound is selected from one of triphenylamine, carbazole and 9- (4-substituted phenyl) -carbazole, and is preferably one of triphenylamine, carbazole and 9- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -9H-carbazole.
The method specifically comprises the following steps:
The molar ratio of 9,9-bis (4-halophenyl) -9H-fluorene to the nitrogen-containing aromatic compound is 2 (0.6-1.6), preferably 2 (0.7-1.4), more preferably 2 (0.8-1.2). In the invention, the quantity of substituted or unsubstituted carbazolyl or nitrogenous phenyl in the product can be adjusted by controlling the dosage ratio of 9,9-bis (4-halophenyl) -9H-fluorene to the nitrogenous aromatic compound, thereby regulating and controlling the product property.
The catalyst is selected from bivalent palladium compounds or monovalent copper salts. When the nitrogen-containing aromatic compound is selected from triphenylamine or 9- (4-substituted phenyl) -carbazole, a divalent palladium compound is used as a catalyst; when the nitrogen-containing aromatic compound is carbazole, cuprous salt is used as a catalyst.
The nitrogen-containing aromatic compound is selected from triphenylamine or 9- (4-substituted phenyl) -carbazole:
the divalent palladium compound is selected from divalent palladium salt or divalent palladium complex, preferably tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) One or more of palladium chloride, palladium acetate, bis (triphenylphosphine) palladium dichloride, bis (triphenylphosphine) palladium acetate and bis (acetylacetone) palladium, and is more preferably Pd (pph) 3 ) 4 。
The divalent palladium compound is acted in the presence of a cocatalyst selected from quaternary ammonium salts, preferably from alkyl ammonium halides, more preferably one or more of tetrabutylammonium bromide (TBAB), tetraethylammonium chloride, tetraethylammonium bromide, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride and tetradecyltrimethylammonium chloride, such as TBAB. In the invention, quaternary ammonium salt used as a phase transfer catalyst is used as a cocatalyst, so that reactants form a homogeneous phase in a solution, and the yield is improved.
The molar ratio of the divalent palladium compound to the cocatalyst is 1 (0.6-1.8), preferably 1 (0.8-1.5), more preferably 1 (1-1.3).
The 9,9-bis (4-halophenyl) -9H-fluorene and the divalent palladium compound have a molar ratio of 2 (0.01-0.06), preferably 2 (0.015-0.05), more preferably 2 (0.02-0.04).
In the reaction solution, the solvent is solvent A, which is one or more selected from ether solvents, ketone solvents and alcohol solvents, preferably one or more selected from tetrahydrofuran, diethyl ether, propylene oxide, methyl isobutyl ketone, cyclohexanone, isophorone, methanol and isopropanol, and more preferably tetrahydrofuran.
In step 1, the molar volume ratio of 9,9-bis (4-halophenyl) -9H-fluorene to solvent A is 2mmol (6-18) mL, preferably 2mmol (8-15) mL, more preferably 2mmol (10-12) mL.
The coupling reaction is carried out under alkaline conditions, preferably by adding an alkaline substance selected from the group consisting of alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide, to the reaction solution.
The reaction is carried out under a protective atmosphere and protected from light, such as under nitrogen or argon. The reaction temperature is 65-105 ℃, preferably 80-90 ℃, and the reaction time is 16-32h, preferably 20-28h.
After the reaction is finished, standing and layering are carried out, the organic phase is separated, and the organic phase is washed by ammonium chloride solution. The organic phase was dried with a solid desiccant and the solvent was removed by vacuum distillation to give a crude product. The crude product is further purified by column chromatography, preferably with silica as the stationary phase and petroleum ether as the mobile phase.
When the nitrogen-containing aromatic compound is carbazole:
the cuprous salt is matched with a ligand for use, and the ligand is selected from a nitrogen-containing ligand or an oxygen-containing ligand, preferably selected from 18-crown-6, phenanthroline and a derivative thereof or ethylene glycol, and more preferably selected from 18-crown-6. The molar ratio of the ligand to the cuprous salt is 1 (0.01-0.06), preferably 1 (0.01-0.04), and more preferably 1 (0.01-0.02).
The cuprous salt is one or more of cuprous iodide, cuprous chloride and cuprous bromide, preferably cuprous iodide and/or cuprous chloride, and more preferably cuprous iodide. The 9,9-bis (4-halophenyl) -9H-fluorene and cuprous salt molar ratio is 2 (0.06-0.8), preferably 2 (0.08-0.5), more preferably 2 (0.1-0.3).
The coupling reaction is carried out under alkaline conditions, preferably by adding an alkaline substance selected from alkali metal carbonates such as potassium carbonate and sodium carbonate to the reaction solution. The molar ratio of the carbazole to the basic substance is 1 (0.7-2.2), preferably 1 (1.0-1.9), and more preferably 1 (1.3-1.6).
In the reaction solution, the solvent is solvent B, which is selected from one or more of urea solvents, sulfone solvents, phenolic solvents and amide solvents, preferably one or more of N, N-dimethylpropyleneurea, dimethyl sulfoxide, p-cresol, N-methylpyrrolidone, N-dimethylaniline, N-dimethylformamide and N, N-dimethylacetamide, and more preferably N, N-dimethylpropyleneurea. In step 1, the molar volume ratio of 9,9-bis (4-halophenyl) -9H-fluorene to solvent B is 2mmol (10-40) mL, preferably 2mmol (16-34) mL, more preferably 2mmol (22-28) mL.
The reaction is carried out under a protective atmosphere and protected from light, such as under nitrogen or argon. The reaction temperature is 160-210 ℃, preferably 180-200 ℃, and the reaction time is 40-55h, preferably 45-50h.
After the reaction is finished, adding a hydrochloric acid solution to quench the reaction, then adding an extracting agent to extract to obtain an organic phase, then drying the organic phase by using a solid drying agent, and removing the solvent by vacuum distillation to obtain a crude product. The crude product was further purified by column chromatography (stationary phase silica, mobile phase petroleum ether) to give intermediate I.
And 2, adding the intermediate product I into a reaction solvent II, adding a lithium reagent at a low temperature, stirring for reaction, and then adding diphenyl phosphorus halide for reaction to prepare an intermediate product II.
The reaction solvent II is selected from ethers such as diethyl ether or tetrahydrofuran, alkanes such as n-hexane, preferably selected from diethyl ether, tetrahydrofuran or n-hexane, more preferably diethyl ether or tetrahydrofuran.
The lithium reagent is selected from alkyl lithium, preferably selected from n-butyl lithium, iso-butyl lithium, tert-butyl lithium, more preferably n-butyl lithium. Preferably, the lithium reagent is added to the reaction system in the form of a lithium reagent solution in a solvent selected from n-hexane, heptane or pentane, such as n-hexane. The lithium reagent has a solubility of 0.8-3.5M, preferably 1.0-3.0M, more preferably 1.2-2.5M. The yield gradually increased as the lithium reagent solubility concentration was gradually optimized. Preferably, the lithium reagent solution is added dropwise.
The molar ratio of the intermediate product I to the lithium reagent is 1 (1.0-2.3), preferably 1 (1.2-2.0), and more preferably 1 (1.4-1.7).
The molar volume ratio of the intermediate product I to the solvent is 1mmol (2-14) mL, preferably 1mmol (3-10) mL, and more preferably 1mmol (4-6) mL.
The reaction temperature is-55 to-100 ℃, preferably-65 to-90 ℃, more preferably-75 to-80 ℃, and the reaction time is 1.0 to 7 hours, preferably 1.5 to 5 hours, more preferably 2.0 to 3 hours. The reaction is carried out under a protective atmosphere, such as nitrogen, argon.
Adding a lithium reagent, stirring for reaction, and then adding diphenyl phosphorus halide for reaction, wherein the diphenyl phosphorus halide is diphenyl phosphorus chloride and/or diphenyl phosphorus bromide, and is preferably diphenyl phosphorus chloride.
The molar ratio of the diphenyl phosphorus halide to intermediate I is 1 (1.0-3.4), preferably 1 (1.5-3.0), more preferably 1 (2.0-2.6), such as 1.
After adding diphenyl phosphorus halide, the mixture reacts for 0.5 to 1 hour at a temperature of between 65 ℃ below zero and 90 ℃ below zero, preferably between 75 ℃ below zero and 80 ℃ below zero. Then reacting for 10-14 hours, such as 12 hours, at 20-30 ℃.
After the reaction is finished, water is added for quenching, and then an extracting agent is added for extraction. The extractant is selected from organic solvents, preferably from halogenated alkanes, more preferably dichloromethane. The organic phase is dried over anhydrous sodium sulfate and the solvent is distilled off at 40-55 c, e.g. 45 c, in vacuo, to give a crude product which is recrystallized from acetone to give intermediate ii.
And 3, adding the intermediate product II into a reaction solvent III, adding an oxidant, stirring for reaction, and performing aftertreatment to obtain the aromatic phosphine oxide compound containing the diphenylfluorene.
The reaction solvent III is selected from one or more of halogenated hydrocarbon solvent, alkane solvent and aromatic hydrocarbon solvent, preferably one or more of dichloromethane, trichloromethane, 1-chloropropane and monochloroethane, and preferably dichloromethane.
The molar volume ratio of the intermediate product II to the reaction solvent III is 1mmol (4-18) mL, preferably 1mmol (6-15) mL, and more preferably 1mmol (8-12) mL.
The oxidant is selected from hydrogen peroxide or peroxyacetic acid, preferably hydrogen peroxide, and more preferably aqueous hydrogen peroxide solution with the mass fraction of 25% -35%.
The molar ratio of the intermediate product II to the oxidant is 1 (4-18), preferably 1 (6-15), and more preferably 1 (8-12).
The reaction temperature is 10 to 30 ℃, preferably 15 to 25 ℃. The reaction is carried out under a protective atmosphere, such as nitrogen, argon.
After the reaction, the reaction solution was worked up. The post-treatment includes extraction, solvent removal and purification.
The extraction is to extract and purify the reaction by using an extractant to obtain an organic phase. The extractant is selected from organic solvents, preferably one or more of halogenated alkane dichloromethane, chloroform and carbon tetrachloride, and more preferably dichloromethane.
And the solvent removal step is to remove the solvent by reduced pressure distillation to obtain a crude product.
The purification is performed by column chromatography, wherein the mobile phase is preferably a mixed solution of ethyl acetate and petroleum ether, and the volume ratio of the ethyl acetate to the petroleum ether is 1:1, so that the aromatic phosphine oxide compound containing the diphenylfluorene is obtained.
The aromatic phosphine oxide compound containing the diphenylfluorene provided by the invention is used for preparing an electroluminescent device.
The electroluminescent device comprises a conductive anode layer, a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode conductive layer.
The invention relates to a preparation method of a luminescent device taking an aromatic phosphine oxide compound containing diphenylfluorene as a luminescent layer material, which specifically comprises the following steps:
1. preparing a conductive anode layer;
the conductive anode layer is prepared on a substrate layer. The conductive anode layer is selected from tin oxide conductive glass (ITO), transparent conductive polymers such as polyaniline, semi-transparent metals such as Au, preferably ITO or semi-transparent metals, more preferably ITO. Preferably, the conductive anode layer is evaporated by vacuum evaporation.
Preferably, the degree of vacuum deposition is 1X 10 -6 mbar, the evaporation rate is set to be 0.1-0.3 nm/s, the evaporation material is indium tin oxide on the glass or plastic substrate, and the anode conductive layer with the thickness of 6-40 nm, preferably 8-30 nm, and more preferably 10-20 nm.
Preferably, the following hole injection layer, hole transport layer, light emitting layer, electron transport layer, electron injection layer and cathode conductive layer are prepared using a vacuum evaporation method.
2. Preparing a hole injection layer;
the hole injection layer is evaporated onto the anode conductive layer to a thickness of 4 to 35nm, preferably 6 to 25nm, more preferably 8 to 15nm, such as 10nm.
The hole injection layer material is selected from molybdenum oxide or poly 3,4-ethylene dioxythiophene: polystyrene sulfonate (PEDOT: PSS), preferably molybdenum oxide, more preferably molybdenum oxide.
3. Preparing a hole transport layer;
the hole transport layer is evaporated onto the hole injection layer to a thickness of 15-65nm, preferably 25-55nm, more preferably 35-45nm, such as 40nm.
The hole transport layer material is selected from one or more of arylamine compounds and carbazole compounds, such as N, N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4,4 ' -diamine (NPB), 9,9' - (1,3-phenyl) di-9H-carbazole (mCP), and preferably mCP.
4. Preparing a luminescent layer;
the light-emitting layer is further evaporated on the hole transport layer to a thickness of 35-75nm, preferably 40-65nm, more preferably 45-55nm, such as 50nm.
The luminescent layer material comprises an aromatic phosphine oxide compound containing diphenylfluorene, preferably, the luminescent layer material also comprises bis [2- ((oxo) diphenylphosphino) phenyl ] ether (DPEPO), and the mass fraction of the DPEPO in the luminescent layer material is 10-30%, preferably 15-25%, such as 20%.
5. Preparing an electron transport layer;
the electron transport layer material is selected from tris (8-hydroxyquinoline) aluminum (Alq 3), 1,3,5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi), 4,7-diphenyl-1,10-phenanthroline (Bphen), 3- (biphenyl-4-yl) -5- (4-tert-butylphenyl) -4-phenyl-4H-1,2,4-Triazole (TAZ) or bis [2- ((oxo) diphenylphosphino) phenyl ] ether (DPEPO), preferably DPEPO. The electron transport layer is evaporated onto the light emitting layer to a thickness of 25 to 55nm, more preferably 35 to 45nm, such as 40nm.
6. Preparing an electron injection layer;
the electron injection layer is evaporated on the electron transport layer to a thickness of 4 to 18nm, preferably 6 to 15nm, more preferably 8 to 12nm, such as 10nm.
The material of the electron injection layer is selected from lithium tetrakis (8-hydroxyquinoline) boron (LiBq) 4 ) Or LiF, preferably LiF.
7. And preparing a cathode conducting layer, and packaging to obtain the thermal excitation delay fluorescence electroluminescent device.
The cathode conductive layer is evaporated on the electron injection layer to a thickness of 4-20nm, preferably 6-15nm, more preferably 8-12nm, such as 10nm.
The cathode conducting layer material is selected from a single metal cathode or an alloy cathode, such as metal Al.
The aromatic phosphine oxide compound containing the diphenylfluorene has good thermal stability and luminescence property, and can improve the electron transport capability in a luminescence layer and optimize the performance of a device when being used as the luminescence layer. The main body material is applied to the electroluminescent device, so that the high-efficiency blue-light thermally-excited delayed fluorescence device is obtained, the luminous efficiency of the device is greatly improved, and the stability of the luminous efficiency is good.
Examples
Example 1
(1) 10mL of tetrahydrofuran was added to the reaction vessel, and argon was introduced to remove dissolved oxygen from the tetrahydrofuran. 9,9-bis (4-bromophenyl) -9H-fluorene (2 mmol), pd (pph) 3 ) 4 (0.025 mmol), tetrabutylammonium bromide TBAB (0.025 mmol) and sodium hydroxide solution (2 mol/L,1.5 mL) were added to oxygen-free tetrahydrofuran and stirred at 80-90 ℃ under argon, protected from light, and then added in portions to triphenylamine (1 mmol). The reaction was then stirred at the same temperature for a further 24 hours.
After the reaction, the mixture was allowed to stand for separation, the organic phase was separated, and the organic phase was washed with an ammonium chloride solution. The organic phase was dried over anhydrous sodium sulfate and the solvent was removed by vacuum distillation to give the crude product. The crude product was further purified by column chromatography using silica as the stationary phase and petroleum ether as the mobile phase to give {4- [9- (4-bromophenyl) -9H-fluorene ] -biphenyl-4 yl } -diphenylamine, structure as follows:
{4- [9- (4-bromophenyl) -9H-fluorene ] -biphenyl-4 yl } -diphenylamine 2mmol was added to anhydrous tetrahydrofuran (5 mL), stirred under argon and cooled to-78 ℃. A solution of n-butyllithium diluted in n-hexane (0.67mL, 2.5 mol/L, ca. 1.6 mmol) was added slowly with vigorous stirring, and stirring was continued at the same temperature for two hours. Then, diphenylphosphoryl chloride (0.4533 mL, ca. 2.4 mmol) was slowly added and the reaction was stirred at 78 ℃ for 30 minutes. The mixture was then stirred at room temperature for 12 hours.
After the reaction, the reaction was quenched with water and extracted with dichloromethane to obtain an organic phase. The organic phase was dried over anhydrous sodium sulfate and the solvent was distilled off in vacuo at 45 ℃ to give the crude product. The crude product was recrystallized from acetone, then the crystalline product (about 1 mmol) was added to 10mL of dichloromethane and stirred in a round bottom flask, then H was added 2 O 2 The solution (30 wt%,1.2mL, about 10 mmol) was slowly added to the round bottom flask and stirred at room temperature. After the reaction was complete, the organic phase was separated and washed with water. The extract was evaporated to dryness to give a white solid, which was driedFurther purifying by column chromatography (stationary phase: silica gel, mobile phase ethyl acetate and petroleum ether mixed solvent, volume ratio of the two is 1:1) to obtain (4- {9- [4- (diphenylphosphinyl) -phenyl]-9H-fluorene-9- } -biphenyl-4-) -diphenylamine (9 TPAFSPO) as compound I.
The obtained compound I is subjected to mass spectrometry, and the flight time mass spectrum data thereof are as follows: m/z (%): 761.28 (100) [ M [) + ]。
The obtained compound I is tested by ultraviolet spectrum and fluorescence spectrum, and the test spectrogram is shown in figure 1.
The thermogravimetric analysis spectrum of the compound I is shown in FIG. 19, the cracking temperature is 405 ℃, and the inset is the differential calorimetry curve of the compound I.
(2) An electroluminescent blue-light device is prepared by taking the obtained mixture of the compound I and bis [2- ((oxo) diphenylphosphino) phenyl ] ether (DPFPO) as a light-emitting layer material, and the method comprises the following steps:
1. putting the glass or plastic substrate cleaned by deionized water into a vacuum evaporation plating instrument for evaporation plating, wherein the vacuum degree is 1 multiplied by 10 -6 mbar, evaporation rate set at 0.1nm s -1 The evaporation material is Indium Tin Oxide (ITO) to obtain an anode conducting layer with the thickness of 10 nm;
2. evaporating a hole injection layer material MoOx on the anode conducting layer to obtain a hole injection layer with the thickness of 10 nm;
3. evaporating a hole transport layer material 9,9' - (1,3-phenyl) di-9H-carbazole (mCP) on the hole injection layer to obtain a hole transport layer with the thickness of 40 nm;
4. and (3) evaporating a luminescent layer material on the hole transport layer: the material of the luminescent layer is a mixture of a compound I and DPFPO, wherein the mass fraction of the DPFPO is 20 percent, and the luminescent layer with the thickness of 50nm is obtained;
5. continuously evaporating DPFPO on the luminescent layer to obtain an electron transport layer with the thickness of 40 nm;
6. evaporating and plating an electron injection layer material LiF on the electron transport layer, wherein the thickness of the electron injection layer is 10 nm;
7. and evaporating a cathode conducting layer which is made of aluminum and has the thickness of 10nm on the electron injection layer to obtain the electro-blue light device 1.
The structure of the electric blue light device 1 in the embodiment is as follows: ITO/MoOx (10 nm)/mcp (40 nm)/(I) DPFPO (20%) 50 nm/(I) (40 nm)/LiF (10 nm)/Al.
Example 2
9,9-bis (4-bromophenyl) -9H-fluorene (2 mmol), carbazole (1 mmol), potassium carbonate (1.5 mmol), 18-crown-6 (0.01 mmol) and cuprous iodide (0.1 mmol) were added to oxygen-free N, N-Dimethylpropylurea (DMPU) (25 mL) (with prior removal of the oxygen from the solvent by nitrogen sparging) and stirred under nitrogen at 190 ℃ for 48H. After the reaction is finished, adding hydrochloric acid solution to quench the reaction, then adding dichloromethane to extract to obtain an organic phase, then drying the organic phase by using anhydrous sodium sulfate, and removing the solvent by vacuum distillation to obtain a crude product. The crude product is further purified by column chromatography (the stationary phase is silicon dioxide, and the mobile phase is petroleum ether) to obtain 9- (4- (9- (4-bromophenyl) -9H-fluoren-9-yl) phenyl) -9H-carbazole.
9- (4- (9- (4-bromophenyl) -9H-fluoren-9-yl) phenyl) -9H-carbazole (1 mmol) was added to dry tetrahydrofuran (5 mL) and stirred under argon and cooled to-78 ℃. A solution of n-butyllithium in n-hexane (0.67mL, 2.5 mol/L, ca. 1.6 mmol) was added slowly with vigorous stirring, and stirring was continued at the same temperature for two hours. Then diphenylphosphoryl chloride (0.45 mL, ca. 2.4 mmol) was added slowly and the reaction was kept stirred at-78 ℃ for 30 minutes. The reaction solution was then stirred at room temperature for 12 hours.
After the reaction, the reaction solution was quenched with water and extracted with dichloromethane to obtain an organic phase. The organic phase was dried over anhydrous sodium sulfate and the solvent was distilled off in vacuo at 45 ℃ to give the crude product. The crude product was recrystallized from acetone, the crystallized solid (1 mmol) was dissolved by adding 10mL of dichloromethane, stirred in a round-bottomed flask, then H was slowly added at room temperature with stirring 2 O 2 (30% by weight, 1.2mL, ca. 10 mmol), after the reaction is complete, the extractant dichloromethane is added and washed with waterAnd extracted three times. The three organic phases were combined and evaporated to dryness to give a white solid which was further purified by column chromatography (stationary phase was silica gel, mobile phase was a mixed solution of ethyl acetate and petroleum ether, volume ratio of the two was 1:1) to give 9- (4- (9- (4- (diphenylphosphoryl) phenyl) -9H-fluoren-9-yl) phenyl) -9H-carbazole (9 CzFSPO) as compound ii.
And carrying out mass spectrum test on the obtained compound II, wherein the flight time mass spectrum data of the compound II are as follows: m/z (%): 683.24 (100) [ M [) + ]；
And testing the obtained compound II by ultraviolet spectrum and fluorescence spectrum, wherein the test spectrogram is shown in figure 2.
The thermogravimetric analysis of the compound II is shown in FIG. 20, which shows that the cracking temperature is 399 ℃. The inset is the differential calorimetry plot for compound ii.
According to the preparation method of the blue electroluminescent device in example 1, a mixture of the compound ii and DPFPO (wherein, the mass fraction of DPFPO is 20%) is used as a luminescent layer material to prepare a blue electroluminescent device 2. The structure is as follows: ITO/MoOx (10 nm)/mcp (40 nm)/(II) DPFPO (20%) 50 nm/(II) (40 nm)/LiF (10 nm)/Al.
Example 3
Compound III was prepared according to the procedure for compound I in example 1.
Wherein 9- (4' - (9- (4-bromophenyl) -9H-fluoren-9-yl) biphenyl-4-yl) -9H-carbazole was prepared according to the procedure for the preparation of {4- [9- (4-bromophenyl) -9H-fluorene ] -biphenyl-4-yl } -diphenylamine in example 1, except that: 5mL of a solution of 9- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -9H-carbazole (1 mmol) in oxygen-free tetrahydrofuran (concentration 0.2 mol/L) was added to the reaction solution in portions in place of triphenylamine. 9- (4' - (9- (4-bromophenyl) -9H-fluoren-9-yl) biphenyl-4-yl) -9H-carbazole:
the difference is also that: 9- (4 '- (9- (4- (diphenylphosphoryl) phenyl) -9H-fluoren-9-yl) biphenyl-4-yl) -9H-carbazole was added to anhydrous tetrahydrofuran (5 mL) in place of {4- [9- (4-bromophenyl) -9H-fluorene ] -biphenyl-4-yl } -diphenylamine in an equimolar amount as described above to prepare 9- (4' - (9- (4- (diphenylphosphoryl) phenyl) -9H-fluoren-9-yl) biphenyl-4-yl) -9H-carbazole (9 PhCzFSPO) as compound III.
And carrying out mass spectrum test on the obtained compound III, wherein the flight time mass spectrum data of the compound III are as follows: m/z (%): 759.27 (100) [ M [) + ]；
And testing the obtained compound III by an ultraviolet spectrum and a fluorescence spectrum, wherein a test spectrogram is shown in figure 3.
According to the preparation method of the electro-blue light device in the example 1, the electro-blue light device 3 is prepared by using a mixture of the compound iii and DPFPO (wherein, the mass fraction of DPFPO is 20%) as a light-emitting layer material. The structure is as follows: ITO/MoOx (10 nm)/mcp (40 nm)/(III) DPFPO (20%) 50 nm/(III) (40 nm)/LiF (10 nm)/Al.
The thermogravimetric analysis spectrum of the compound III is shown in FIG. 21, from which it is found that the cracking temperature is 405 ℃. The inset is the differential calorimetry plot of compound iii.
Examples of the experiments
Experimental example 1
As shown in fig. 4, 9 and 14, it can be seen that the turn-on voltages of the electro-blue light devices 1 to 3 prepared in examples 1 to 3 are 3.8V, 3.5V and 3.8V, respectively. (the on-off voltage is 1cd/m luminance 2 Voltage of time)
Experimental example 2
As shown in fig. 5, 10 and 15, the luminance-current efficiency relationship curves of the blue electroluminescent devices 1 to 3 prepared in test examples 1 to 3 show:
the electroluminescent blue light device 1 has a luminance of 11cd m -2 When the current efficiency reaches the maximum value of 27.6 cd.A -1 。
The electroluminescent blue light device 2 has a luminance of 12cd m -2 When the current efficiency reaches the maximum value of 25.9 cd.A -1 。
The electroluminescent blue light device 3 has a luminance of 11cd m -2 When the current efficiency reaches the maximum value of 26.3 cd.A -1 。
Experimental example 3
As shown in fig. 6, 11 and 16, the luminance-power efficiency relationship curves of the blue electroluminescent devices 1 to 3 prepared in test examples 1 to 3 were confirmed,
the electroluminescent blue light device 1 has a luminance of 11cd m -2 When the power efficiency reaches the maximum value of 17.5 lm.W -1 。
The electroluminescent blue light device 2 has a luminance of 12cd m -2 When the power efficiency reaches the maximum value of 25.4 lm.W -1 。
The electroluminescent blue light device 3 has a luminance of 11cd m -2 When the power efficiency reaches the maximum value of 24.6 lm.W -1 。
Experimental example 4
As shown in fig. 7, 12 and 17, the luminance-external quantum efficiency relationship curves of the electro-blue devices prepared in test examples 1 to 3 show that,
the electroluminescent blue light device 1 has a luminance of 11cd m -2 Then, the maximum external quantum efficiency of 27.1% is obtained.
The electroluminescent blue light device 2 has a luminance of 12cd m -2 Then, the maximum external quantum efficiency of 26.7% is obtained.
The electroluminescent blue light device 3 has a luminance of 11cd m -2 Then, a maximum external quantum efficiency of 32.3% was obtained.
Experimental example 5
The electroluminescence spectra of the electroluminescent blue devices 1 to 3 prepared in test examples 1 to 3 are shown in fig. 8, 13 and 18, respectively.
From the above data, the electroluminescence peaks of the electro-blue devices prepared in examples 1 to 3 were 478nm, 475nm and 477nm, respectively.
The invention has been described in detail with reference to specific embodiments and/or illustrative examples and the accompanying drawings, which, however, should not be construed as limiting the invention. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. An aromatic phosphine oxide compound containing diphenylfluorene, which has the following structure:
wherein X is selected from substituted or unsubstituted carbazolyl or nitrogenated phenyl.
2. The compound according to claim 1, selected from one of the following compounds:
3. the preparation method of the aromatic phosphine oxide compound containing the diphenylfluorene is characterized in that 9,9-bis (4-halophenyl) -9H-fluorene is used as a raw material, and is firstly subjected to coupling reaction with a nitrogen-containing aromatic compound, then is subjected to nucleophilic substitution with diphenyl phosphorus halide, and is oxidized to obtain the aromatic phosphine oxide compound containing the diphenylfluorene.
4. The method of claim 1,
the 9,9-bis (4-halophenyl) -9H-fluorene is selected from 9,9-bis (4-chlorophenyl) -9H-fluorene, 9,9-bis (4-bromophenyl) -9H-fluorene or 9,9-bis (4-iodophenyl) -9H-fluorene, preferably 9,9-bis (4-bromophenyl) -9H-fluorene;
the nitrogen-containing aromatic compound is selected from one of triphenylamine, carbazole and 9- (4-substituted phenyl) -carbazole, and is preferably one of triphenylamine, carbazole and 9- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -9H-carbazole.
5. The method according to claim 3 or 4, characterized in that it comprises in particular the steps of:
step 1, adding a catalyst into a reaction solution containing 9,9-bis (4-halophenyl) -9H-fluorene, adding a nitrogen-containing aromatic compound, and carrying out heating coupling reaction to prepare an intermediate product I;
step 2, adding the intermediate product I into a reaction solvent II, adding a lithium reagent at a low temperature, stirring for reaction, and then adding diphenyl phosphorus halide for reaction to prepare an intermediate product II;
and 3, adding the intermediate product II into a reaction solvent III, adding an oxidant, stirring for reaction, and performing aftertreatment to obtain the aromatic phosphine oxide compound containing the diphenylfluorene.
6. The method according to claim 5, wherein in step 1, the catalyst is selected from a divalent palladium compound or a monovalent copper salt;
when the nitrogen-containing aromatic compound is selected from triphenylamine or 9- (4-substituted phenyl) -carbazole, a divalent palladium compound is used as a catalyst; when the nitrogen-containing aromatic compound is carbazole, cuprous salt is used as a catalyst.
7. The method according to claim 5, wherein in step 1, the molar ratio of 9,9-bis (4-halophenyl) -9H-fluorene to nitrogen-containing aromatic compound is 2 (0.6-1.6), preferably 2 (0.7-1.4), more preferably 2 (0.8-1.2).
8. The method according to claim 5, wherein, in step 2,
the reaction solvent II is selected from ethers such as diethyl ether or tetrahydrofuran, alkanes such as n-hexane, preferably selected from diethyl ether, tetrahydrofuran or n-hexane, more preferably diethyl ether or tetrahydrofuran;
the lithium reagent is selected from alkyl lithium, preferably selected from n-butyl lithium, iso-butyl lithium, tert-butyl lithium, more preferably n-butyl lithium.
9. The method according to claim 5, wherein in step 3, the oxidizing agent is selected from hydrogen peroxide or peracetic acid, preferably hydrogen peroxide, more preferably an aqueous solution of hydrogen peroxide with a mass fraction of 25% to 35%; the molar ratio of the intermediate product II to the oxidant is 1 (4-18), preferably 1 (6-15), and more preferably 1 (8-12).
10. An electroluminescent device, characterized in that the luminescent layer material of the electroluminescent device comprises one or more of the aromatic phosphine oxide compounds containing diphenylfluorene as described in claim 1;
the electroluminescent device comprises a conductive anode layer, a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode conductive layer.
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| CN113801102A (en) * | 2021-10-11 | 2021-12-17 | 上海交通大学 | Phenazinyl-based compound and preparation method and application thereof |
| CN114409700A (en) * | 2020-10-28 | 2022-04-29 | 黑龙江大学 | Thermal excitation delayed fluorescence bipolar host material based on diphenyl sulfide, synthetic method and application thereof |
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| CN102911658A (en) * | 2012-11-02 | 2013-02-06 | 黑龙江大学 | Nine-site functional fluorenyl aromatic single-phosphine oxide electroluminescent material and preparation method thereof |
| CN114409700A (en) * | 2020-10-28 | 2022-04-29 | 黑龙江大学 | Thermal excitation delayed fluorescence bipolar host material based on diphenyl sulfide, synthetic method and application thereof |
| CN113801102A (en) * | 2021-10-11 | 2021-12-17 | 上海交通大学 | Phenazinyl-based compound and preparation method and application thereof |
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