CN115583976A - Bivalent platinum complex with adjustable luminescence spectrum, preparation method and application of bivalent platinum complex as yellow phosphorescent material in organic photoelectric device - Google Patents
Bivalent platinum complex with adjustable luminescence spectrum, preparation method and application of bivalent platinum complex as yellow phosphorescent material in organic photoelectric device Download PDFInfo
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- CN115583976A CN115583976A CN202110750711.0A CN202110750711A CN115583976A CN 115583976 A CN115583976 A CN 115583976A CN 202110750711 A CN202110750711 A CN 202110750711A CN 115583976 A CN115583976 A CN 115583976A
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- Prior art keywords
- complex
- ethyl acetate
- synthesis
- bipyridine
- yellow
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000000463 material Substances 0.000 title claims abstract description 63
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000001748 luminescence spectrum Methods 0.000 title description 9
- 239000003446 ligand Substances 0.000 claims abstract description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 114
- -1 3,3,3-trifluoropropyl Chemical group 0.000 claims description 79
- 230000015572 biosynthetic process Effects 0.000 claims description 30
- 238000003786 synthesis reaction Methods 0.000 claims description 29
- 239000003480 eluent Substances 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 25
- 238000001816 cooling Methods 0.000 claims description 22
- 239000000543 intermediate Substances 0.000 claims description 22
- 238000010898 silica gel chromatography Methods 0.000 claims description 22
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 12
- 239000012074 organic phase Substances 0.000 claims description 12
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- RMHQDKYZXJVCME-UHFFFAOYSA-N 2-pyridin-4-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=NC=C1 RMHQDKYZXJVCME-UHFFFAOYSA-N 0.000 claims description 10
- 239000012043 crude product Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000003208 petroleum Substances 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 230000005587 bubbling Effects 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- VVAOPCKKNIUEEU-PHFPKPIQSA-L dichloro(cycloocta-1,5-diene)platinum(ii) Chemical compound Cl[Pt]Cl.C\1C\C=C/CC\C=C/1 VVAOPCKKNIUEEU-PHFPKPIQSA-L 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000004912 1,5-cyclooctadiene Substances 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 239000008346 aqueous phase Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000005859 coupling reaction Methods 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 239000001632 sodium acetate Substances 0.000 claims description 6
- 235000017281 sodium acetate Nutrition 0.000 claims description 6
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 claims description 6
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000012267 brine Substances 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 238000010791 quenching Methods 0.000 claims description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 5
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 4
- STUASDSPZRHRDI-UHFFFAOYSA-N ClC1=NC(=CC=C1NC(C)C)C Chemical compound ClC1=NC(=CC=C1NC(C)C)C STUASDSPZRHRDI-UHFFFAOYSA-N 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 238000007363 ring formation reaction Methods 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 125000004860 4-ethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000004861 4-isopropyl phenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 150000003058 platinum compounds Chemical class 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 2
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 claims description 2
- YRAJNWYBUCUFBD-UHFFFAOYSA-N 2,2,6,6-tetramethylheptane-3,5-dione Chemical compound CC(C)(C)C(=O)CC(=O)C(C)(C)C YRAJNWYBUCUFBD-UHFFFAOYSA-N 0.000 claims description 2
- IRQKFOGCFLZKNL-UHFFFAOYSA-N 2,6-dichloro-4-pyridin-2-ylpyridine Chemical compound ClC1=NC(Cl)=CC(C=2N=CC=CC=2)=C1 IRQKFOGCFLZKNL-UHFFFAOYSA-N 0.000 claims description 2
- RTZZCYNQPHTPPL-UHFFFAOYSA-N 3-nitrophenol Chemical compound OC1=CC=CC([N+]([O-])=O)=C1 RTZZCYNQPHTPPL-UHFFFAOYSA-N 0.000 claims description 2
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- 238000006443 Buchwald-Hartwig cross coupling reaction Methods 0.000 claims description 2
- LZQAQTILNGYOLX-UHFFFAOYSA-N CC(C)C1=CC=CC(C(C)C)=C1NC1=CC=C(C)N=C1Cl Chemical compound CC(C)C1=CC=CC(C(C)C)=C1NC1=CC=C(C)N=C1Cl LZQAQTILNGYOLX-UHFFFAOYSA-N 0.000 claims description 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000006887 Ullmann reaction Methods 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 2
- 229910052805 deuterium Inorganic materials 0.000 claims description 2
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 239000012634 fragment Substances 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000002883 imidazolyl group Chemical group 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 claims description 2
- 230000000155 isotopic effect Effects 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims description 2
- 230000005693 optoelectronics Effects 0.000 claims description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000003222 pyridines Chemical class 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000002827 triflate group Chemical group FC(S(=O)(=O)O*)(F)F 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims 4
- 238000003756 stirring Methods 0.000 claims 3
- 229910052763 palladium Inorganic materials 0.000 claims 2
- 229920006395 saturated elastomer Polymers 0.000 claims 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 239000007983 Tris buffer Substances 0.000 claims 1
- 125000004431 deuterium atom Chemical group 0.000 claims 1
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 claims 1
- 239000011780 sodium chloride Substances 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 14
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 abstract description 10
- 238000005286 illumination Methods 0.000 abstract description 6
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 36
- 239000010410 layer Substances 0.000 description 34
- 238000005481 NMR spectroscopy Methods 0.000 description 19
- 238000004020 luminiscence type Methods 0.000 description 16
- 238000001228 spectrum Methods 0.000 description 16
- 238000001704 evaporation Methods 0.000 description 14
- 230000008020 evaporation Effects 0.000 description 13
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 10
- 239000004926 polymethyl methacrylate Substances 0.000 description 10
- 239000010408 film Substances 0.000 description 7
- 230000005525 hole transport Effects 0.000 description 7
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 239000011368 organic material Substances 0.000 description 7
- 238000000295 emission spectrum Methods 0.000 description 6
- 238000001819 mass spectrum Methods 0.000 description 6
- 150000003057 platinum Chemical class 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000004611 spectroscopical analysis 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
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004770 highest occupied molecular orbital Methods 0.000 description 3
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 3
- KLFKZIQAIPDJCW-GPOMZPHUSA-N 1,2-dihexadecanoyl-sn-glycero-3-phosphoserine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP(O)(=O)OC[C@H](N)C(O)=O)OC(=O)CCCCCCCCCCCCCCC KLFKZIQAIPDJCW-GPOMZPHUSA-N 0.000 description 2
- CINYXYWQPZSTOT-UHFFFAOYSA-N 3-[3-[3,5-bis(3-pyridin-3-ylphenyl)phenyl]phenyl]pyridine Chemical compound C1=CN=CC(C=2C=C(C=CC=2)C=2C=C(C=C(C=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)=C1 CINYXYWQPZSTOT-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001793 charged compounds Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001194 electroluminescence spectrum Methods 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000004806 packaging method and process Methods 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
- 238000005086 pumping Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
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- GLGNXYJARSMNGJ-VKTIVEEGSA-N (1s,2s,3r,4r)-3-[[5-chloro-2-[(1-ethyl-6-methoxy-2-oxo-4,5-dihydro-3h-1-benzazepin-7-yl)amino]pyrimidin-4-yl]amino]bicyclo[2.2.1]hept-5-ene-2-carboxamide Chemical compound CCN1C(=O)CCCC2=C(OC)C(NC=3N=C(C(=CN=3)Cl)N[C@H]3[C@H]([C@@]4([H])C[C@@]3(C=C4)[H])C(N)=O)=CC=C21 GLGNXYJARSMNGJ-VKTIVEEGSA-N 0.000 description 1
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- YAELXYZSNJSOCR-UHFFFAOYSA-N 2-pyridin-2-yl-5-[7-(6-pyridin-2-ylpyridin-3-yl)triphenylen-2-yl]pyridine Chemical group N1=CC=CC=C1C1=CC=C(C=2C=C3C4=CC=CC=C4C4=CC(=CC=C4C3=CC=2)C=2C=NC(=CC=2)C=2N=CC=CC=2)C=N1 YAELXYZSNJSOCR-UHFFFAOYSA-N 0.000 description 1
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- WXAIEIRYBSKHDP-UHFFFAOYSA-N 4-phenyl-n-(4-phenylphenyl)-n-[4-[4-(4-phenyl-n-(4-phenylphenyl)anilino)phenyl]phenyl]aniline Chemical group C1=CC=CC=C1C1=CC=C(N(C=2C=CC(=CC=2)C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC(=CC=2)N(C=2C=CC(=CC=2)C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC=CC=2)C=C1 WXAIEIRYBSKHDP-UHFFFAOYSA-N 0.000 description 1
- CUQGKGMUSQKHFO-UHFFFAOYSA-N 9-(6-carbazol-9-ylpyridin-2-yl)carbazole Chemical group C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=CC(N2C3=CC=CC=C3C3=CC=CC=C32)=N1 CUQGKGMUSQKHFO-UHFFFAOYSA-N 0.000 description 1
- NSXJEEMTGWMJPY-UHFFFAOYSA-N 9-[3-(3-carbazol-9-ylphenyl)phenyl]carbazole Chemical group C12=CC=CC=C2C2=CC=CC=C2N1C1=CC(C=2C=CC=C(C=2)N2C3=CC=CC=C3C3=CC=CC=C32)=CC=C1 NSXJEEMTGWMJPY-UHFFFAOYSA-N 0.000 description 1
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- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
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- UIJLKECZHOSSHF-UHFFFAOYSA-N diphenyl-bis(4-pyridin-3-ylphenyl)silane Chemical compound C1=CC=CC=C1[Si](C=1C=CC(=CC=1)C=1C=NC=CC=1)(C=1C=CC(=CC=1)C=1C=NC=CC=1)C1=CC=CC=C1 UIJLKECZHOSSHF-UHFFFAOYSA-N 0.000 description 1
- DKHNGUNXLDCATP-UHFFFAOYSA-N dipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile Chemical group C12=NC(C#N)=C(C#N)N=C2C2=NC(C#N)=C(C#N)N=C2C2=C1N=C(C#N)C(C#N)=N2 DKHNGUNXLDCATP-UHFFFAOYSA-N 0.000 description 1
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- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 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
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- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
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Images
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0086—Platinum compounds
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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Abstract
The invention belongs to the technical field of organic electroluminescent materials, and particularly relates to a preparation method of an organic metal platinum complex, a luminescent device and application thereof. The bipyridine N ^ C coordination structure is introduced into a ligand structure of a divalent platinum complex, the obtained tetradentate ligand coordinated platinum heterocomplex yellow phosphorus light emission peak is controlled between 550 and 570nm, the half-peak width is adjustable between 36 and 147nm, and the tetradentate ligand coordinated platinum heterocomplex yellow phosphorus light emission peak is a spectrum-adjustable high-efficiency yellow phosphorus material, can be used for preparing electroluminescent applications related to yellow phosphorus light emission devices, and can also be combined with blue light devices to manufacture white phosphorus light devices and be applied to illumination or display.
Description
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to a divalent platinum complex, a preparation method thereof, and application of the divalent platinum complex as an electroluminescent material in an organic photoelectric device.
Background
Organic light-emitting diodes (OLEDs) can be applied to the next generation illumination and display field due to their characteristics of surface light emission, flexibility, lightness, thinness, proximity to sunlight, low blue light, no glare hazard, and the like. In terms of luminescence, yellow is a "combined" color, which is not one of the three primary colors of "RGB", and is a constituent color of equal amounts of red light and green light, so in the color science, yellow phosphor light is formed by filtering blue light out of white phosphor light, and is also a complementary color auxiliary color of blue light. Therefore, the blue light and yellow phosphor can be used to cooperate with each other to form a white phosphor light source with high efficiency and high stability. Therefore, the Huang Linguang high efficiency luminescent material and device have practical application value in display, illumination and special yellow light fixture. The organic bivalent platinum complex coordinated by the tetradentate ligand has the characteristics of good spectrum regulation performance, high efficiency and high potential stability, so that the organic light-emitting diode device with a proper light-emitting spectrum can be developed and prepared. Specific spectrum controllability characteristics can be referred to the published technical literature: triple Excited-State Engineering of Phosphorescent Pt (II) Complexes Yipei Wu, xiao Tan, anqi Lv, feiling Yu, huili Ma, kang Shen, zhengyi Sun, fei Chen, zhi-Kuan Chen, and Xiao-Chun Hang J.Phys.Chem.Lett.2019,10,5105-5110. The specific divalent platinum complex can be used for preparing a stable light-emitting device, and the following technical documents can be referred: effective and stable organic light-emitting devices emitting phosphor arrays Linyu Cao, kody Klimes, yunlong Ji, tyler Fleetham and Jianan Li, nature Photonics 2021,15,230-237.
Patent CN 112125932A discloses Pt-C-containing py Structural high performance yellow phosphorescent materials, wherein py The coordinated pyridine is shown as an electron donor in the whole molecule, the design has the characteristic of reverse electrical application of functional groups, the internal complex structure is three continuous 5-6-membered platinum metal rings, the structure generally has larger torsion resistance, so that the characteristic of molecular monomer luminescence is shown, and the 5-6-5-membered platinum metal rings can also be in a travel aggregation state luminescence level at higher concentration besides the molecular monomer luminescence, so that the luminescence property at lower photon energy is obtained, and specific theories and potential functional change characteristics thereof can refer to published technical documents: binding triple Excited States and manipulating Blue Light Emission of Neutral clover plate (II) complex consistent You, fang Xia, yue Zhao, yin Zhang, yongjian Sheng, yipiei Wu, xiao-Chun Hang, fei Chen, huili Ma, kang Shen, zhengyi Sun, takahiro Ueba, satoshi Kera, cong Zhang, honghai Zhang, zhuan Chen, and Wei Huang J.Phys.m.Lett.2018, 9,2285-2292.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the bivalent platinum complex can be used as a high-efficiency Huang Linguang luminescent material, the half-peak width of a luminescent spectrum of the material can be greatly adjusted, and the bivalent platinum complex has a huge application space in the fields of display and illumination.
The divalent platinum complex disclosed by the invention has a structure shown in a formula (I):
wherein R is a 、R c And R d Each independently is a mono-or di-substituent, and R a 、R c And R d Each independently selected from a single atom substituent or a multiple atom substituent; r b 、R e Are substituents each independently containing at least 1 carbon atom; the monoatomic substituent includes a hydrogen atom, an isotope atom thereof, or a halogen atom; the polyatomic substituent is an alkyl or aryl substituent with 1 to 14 carbon atoms, and comprises alkyl, aryl-substituted alkyl, fluorine-substituted alkyl, aryl, alkyl-substituted aryl, aryl-substituted aryl, or the substituent containing isotopic atoms.
Further, R a 、R c And R d May be each independently selected from a hydrogen atom, a deuterium atom, a fluorine atom; r a 、R b 、R c 、R d 、R e Selected from deuterated or non-deuterated methyl, benzyl, diphenylmethyl, triphenylmethyl; ethyl, 2-phenylethyl, 2,2-phenylethyl, 2,2,2-trifluoroethyl; propyl, isopropyl, 3,3,3-trifluoropropyl, 1,1,1,3,3,3-hexafluoro-2-propyl; n-butyl, isobutyl, hexafluoroisobutyl, tert-butyl; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl; phenyl, 2-methylphenyl, 2-isopropylphenyl, 2-ethylphenyl, 4-methylphenyl, 4-isopropylphenyl, 4-ethylphenyl, 4-tert-butylphenyl, 2,3-dimethylphenyl, 2,3-diethylphenyl, 2,3-diisopropylphenyl, 2,3-diisobutylphenyl, 2,3-dicyclohexylphenyl, 2,3-dicyclopropylphenyl, 2,3-dicyclobutylphenyl-a group, -dicyclopentylphenyl, -dimethylphenyl, -diethylphenyl, -diisopropylphenyl, -diisobutylphenyl, -dicyclohexylphenyl, -dicyclopropylphenyl, -dicyclobutylphenyl, -dicyclopentylphenyl, -dimethylphenyl, -diethylphenyl, -diisopropylphenyl, -diisobutylphenyl, -dicyclohexylphenyl, -dicyclopropylphenyl, -dicyclopentylphenyl, -dimethylphenyl, -diethylphenyl, -diisopropylphenyl, -diisobutylphenyl, -dicyclopropylphenyl, -dicyclopentylphenyl, -tetramethylphenyl, -trimethylphenyl, -triethylphenyl, -triisopropylphenyl, -triisobutylphenyl, -tricyclohexylphenyl, -tricyclopropylphenyl.
The divalent platinum complex is selected from the structure of one of the following complexes 1-90:
further, R in the above divalent platinum complex a 、R c And R e Is a hydrogen atom, R e Selected from alkyl and aryl; r a 、R c And R d Is a hydrogen atom, R b Selected from alkyl and aryl groups.
The invention also provides a general synthesis method of the divalent platinum complex, which comprises the following specific steps:
the first step is as follows: through 4-R a Substituted pyridyl-2,6-dichloro, bromo, iodo or triflate substituted pyridines are the basic units to which they are coupled;
the second step is that: carrying out two coupling reactions to respectively obtain intermediates coupled with corresponding fragments, wherein the two coupling reactions comprise any one of Ullmann coupling, buchwald-hartwig coupling reaction or similar coupling reaction;
the third step: imidazole ring closure reaction, specifically, under the action of a fluorine-containing anion salt, performing one-step condensation cyclization of a coupled intermediate and trialkyl orthoformate to obtain a precursor of a final product ligand, wherein the fluorine-containing anion of the precursor comprises hexafluorophosphate negative ions, tetrafluoroborate negative ions, trifluoromethanesulfonic acid negative ions or trifluoromethanesulfonimide negative ions;
the fourth step: divalent platinum complex synthesis: the divalent platinum complex can be directly obtained by reacting the ligand precursor with the divalent platinum complex at a temperature of more than 80 ℃, wherein the divalent platinum compound can be potassium tetrachloroplatinate, (1,5-cyclooctadiene) platinum dichloride, platinum dichloride and the like.
In addition, the invention also provides application of the divalent platinum complex as an electroluminescent material or a photoluminescent material.
Optionally, the divalent platinum complex provided by the invention can be applied to an organic photoelectric device as a yellow phosphorescent light-emitting material or a phosphorescent light-emitting material.
The invention has the beneficial effects that: compared with the prior art, the invention provides the yellow phosphorus light luminescent material with a broad spectrum by introducing bipyridine into the ligand of the bivalent platinum complex, wherein one pyridine ring forms a C-Pt metal bond with a metal center through a carbon atom. In the embodiment of the invention, the disclosed bivalent platinum complex molecule coordinated by the neutral tetradentate ligand containing the bipyridyl structure can emit yellow phosphorescence as a phosphorescent luminescent material, the wavelength peak value of the yellow phosphorescence is in the range of 550-580 nm, the luminescent range can be covered in the range of 510-700, and the bivalent platinum complex molecule has good stability and high efficiency, and is completely suitable for being used as an organic yellow phosphorescence luminescent material in OLED related products. From the patent embodiment, when the substituent on the pyridylimidazole is 2,6-diisopropylphenyl, the molecule presents monomolecular luminescent performance due to steric hindrance and vibration limitation effects; when the isopropyl group is used, the aggregation luminescence effect is achieved, so that the wide-spectrum yellow luminescence can be regulated and controlled; for an explanation of the theory of relevance, reference may be made to the publications Lu Zhu, wentao Xie, chunyue Qian, wang Xie, kang Shen, anqi Lv, huili Ma, hongbo Li, xiao-Chun Handg, wenqi Li, shi-Jian Su, and Wei Huang Brand. Tetradent Pt (II) Complexes for Spectrum-Stable Deep-Blue and Whectrolens approach adv. Optical Mat.2020, 2000406. And the free N atom ortho substituent in the bipyridyl N ^ C coordination structure has a regulation and control function on the monomolecular luminescence of the luminescence spectrum, namely the freely rotating phenyl can widen the luminescence spectrum, so that the span of a yellow light-emitting region is regulated and controlled. Therefore, the three examples of the patent realize the change of the spectrum of the Huang Linguang in the solid state in the range of 39-147 nm of half-peak width. In addition, the bivalent platinum complex provided by the invention is easy to prepare, sublimate and purify, is dissolved in a common organic solvent, and can be suitable for device manufacturing procedures processed by an evaporation method and a solution method. The luminescent performance of the material has the characteristics of low energy and good color purity, is comprehensively superior to various fluorescent materials in the prior art, and simultaneously achieves the functions of emitting yellow phosphorus light color and improving the performance of devices; the divalent complex is used as a luminescent material, and the CIE coordinates and the luminous efficiency of the divalent complex meet the requirements of flat panel display. Meanwhile, the series of yellow phosphorescent materials can be used as auxiliary photochromic materials of blue light to form a white phosphorescent light source with high efficiency and high stability, and have great development potential in the fields of display and illumination.
Drawings
FIG. 1 is a graph of the luminescence spectrum of complex 6 in solution and in thin films according to an embodiment of the present invention;
FIG. 2 is a graph of the luminescence spectrum of complex 15 in solution and in thin films in accordance with an embodiment of the present invention;
FIG. 3 is a graph of the luminescence spectrum of complex 81 in solution and in thin films according to an embodiment of the present invention;
FIG. 4 is a graph of the UV-VIS absorption spectrum of complex 6 in an embodiment of the present invention;
FIG. 5 is a graph of the UV-VIS absorption spectrum of complex 15 in an embodiment of the present invention;
FIG. 6 is a drawing of complex 6 in an embodiment of the present invention 1 H NMR nuclear magnetic spectrum;
FIG. 7 is a drawing of complex 15 in an embodiment of the present invention 1 H NMR nuclear magnetic spectrum;
FIG. 8 is a graph depicting the purity of complex 15 in accordance with an embodiment of the present invention;
FIG. 9 is a mass spectrum of complex 15 in accordance with an embodiment of the present invention;
FIG. 10 is a mass spectrum of a complex 81 according to an embodiment of the present invention;
FIG. 11 is a cross-sectional view of an OLED device in an embodiment of the present invention;
FIG. 12 shows the emission spectrum of a yellow phosphor device using the complex 6, 15, 81 according to the embodiment of the present invention;
FIG. 13 is a CIE coordinate diagram of the emission spectrum of a yellow phosphor device using complexes 6, 15, 81 according to an embodiment of the present invention
FIG. 14 is a graph of the external quantum efficiency of yellow phosphorus optical devices using complexes 6, 15, 81 according to embodiments of the present invention;
Detailed Description
The invention is further illustrated by the following examples:
in the following specific examples of the present invention, the complex 6, the complex 15, and the complex 81 are taken as examples to specifically describe the synthesis method, properties, and performance of the divalent platinum complex provided by the present invention when used as a light-emitting material.
The various methods of preparation of the compounds provided herein are exemplary. These methods are intended to illustrate the various methods of preparation, but are not intended to be limiting to any particular method, and the temperature, catalyst, concentration, reactant composition, and other process conditions may vary. The series of complexes can be synthesized by the route of the invention, and the method comprises the following steps:
further, in the examples, in CDCl 3 Or DMSO-d 6 In solution, recorded by Varian liquid NMR 1 HNMR (hydrogen nuclear magnetic resonance) and 13 the C NMR (carbon nuclear magnetic resonance) spectrum is 300, 400 or 500MHz and the chemical shifts are based on residual protonated solvent. If CDCl is used 3 As a solvent, tetramethylsilane (δ =0.00 ppm) was used as an internal reference for recording 1 H NMR (hydrogen nuclear magnetic resonance) spectroscopy; using CDCl 3 (δ =77.00 ppm) is recorded as the internal reference 13 C NMR (carbon nuclear magnetic resonance) spectroscopy. If DMSO-d is used 6 As solvent, residual H is used 2 O (δ =3.33 ppm) was recorded as an internal reference 1 H NMR (hydrogen nuclear magnetic resonance) spectroscopy; using DMSO-d 6 (δ =39.52 ppm) is recorded as an internal reference 13 C NMR (carbon nuclear magnetic resonance) spectroscopy. The following abbreviations are used for explanation 1 Multiplicity of H NMR (hydrogen nuclear magnetic resonance): s = singlet, d = doublet, t = triplet, q = quadrate, p = penta, m = multiline, br = wide.
EXAMPLE 1 Complex 6 and preparation thereof
Synthesis of 2' -chloro-6 ' - (3-nitrophenoxy) -2,4' -bipyridine:
to a 75mL sealed tube with a magnetic rotor were added 2',6' -dichloro-2,4 ' -bipyridine (1.37g, 4.4 mmol), 3-nitrophenol (0.56g, 4 mmol), 2,2,6,6-tetramethyl-3,5-heptanedione (590mg, 3.2mmol), cuprous bromide (58mg, 0.4 mmol), cesium carbonate (3.26g, 10mmol), and N, N-dimethylformamide (20 mL), and the resulting mixture was bubbled with nitrogen for 10 minutes and then heated to 130 ℃ and stirred for 36 hours. Cooling to room temperature, adding water to quench the reaction, extracting with ethyl acetate, combining organic phases, washing with a proper amount of saturated sodium chloride aqueous solution, and then adding anhydrous sodium sulfate for drying. The solvent was removed by distillation under the reduced pressure, and the resulting crude product was isolated and purified by silica gel column chromatography with petroleum ether/ethyl acetate = 25: 1 as eluent to give a white solid in 46% yield.
Synthesis of 2' - (3-nitrophenoxy) -6' - (prop-1-en-2-yl) -2,4' -bipyridine:
to a 5mL lock tube with a magnetic rotor was added 2' -chloro-6 ' - (3-nitrophenoxy) -2,4' -bipyridine (107.9 mg, 0.33mmol), 4,4,5,5-tetramethyl-2- (prop-1-en-2-yl) -1,3,2-dioxaborane (139mg, 0.825 mmol), tetrakistriphenylphosphine palladium (12mg, 0.01mmol), potassium carbonate (69mg, 0.5 mmol), ethylene glycol dimethyl ether (0.75 mL), and water (0.75 mL), and the resulting mixture was bubbled with nitrogen for 10 minutes and then heated to 100 ℃ and stirred overnight. Cooling to room temperature, adding water to quench the reaction, extracting with ethyl acetate, combining organic phases, washing with a proper amount of saturated sodium chloride aqueous solution, and then adding anhydrous sodium sulfate for drying. The solvent was removed by distillation under the reduced pressure, and the resulting crude product was isolated and purified by silica gel column chromatography with petroleum ether/ethyl acetate = 25: 1 as eluent to give a white solid with a yield of 98%.
3- ((6 '-isopropyl- [2,4' -bipyridine)]-2' -yl) oxy)) aniline:
to a 50mL round bottom flask with magnetic rotator, 2' - (3-nitrophenoxy) -6' - (prop-1-en-2-yl) -2,4' -bipyridine (108mg, 0.325mmol), pd/C (10 mg), methanol (8 mL) and tetrahydrofuran (8 mL) was stirred at room temperature under an atmosphere of hydrogen for 24 hours. After the reaction is finished, the reaction system is subjected to suction filtration treatment and washed by a large amount of ethyl acetate, the filtrate obtained by suction filtration is subjected to reduced pressure distillation to remove the solvent, the obtained crude product is separated and purified by silica gel column chromatography, and the eluent is petroleum ether and ethyl acetate = 25: 1, so that white solid is obtained, and the yield is 78%.
Synthesis of pyridine diamine derivatives 1 to 4:
addition of intermediate 3- ((6 '-isopropyl- [2,4' -bipyridine) to one sealed tube in glove box]-2' -yl) oxy) aniline (305mg, 1mmol), 2-chloro-N-isopropyl-6-methylpyridin-3-amine (202mg, 1.1mmol), tris (dibenzylideneacetone) dipalladium (45.5mg, 0.05mmol), 1,1' -binaphthyl-2,2 ' -bis-diphenylphosphine (31.1mg, 0.5mmol), sodium tert-butoxide (144mg, 1.5mmol), and toluene (4 mL). After bubbling the mixture for 15 minutes, the mixture was heated at 130 ℃ for 20 hours. After cooling, ethyl acetate was added, and the mixture was filtered. Extracting the aqueous phase with ethyl acetate, mixing the organic phases, washing with brine, and adding anhydrous Na 2 SO 4 And (5) drying. The obtained solution was purified by silica gel chromatography using PE: EA = 6: 1 as an eluent, and the eluent was spin-dried to obtain the pyridine diamine derivative 1-4 (yellow viscous liquid, yield 90%).
Synthesis of carbene hexafluorophosphate 1-5:
to one sealed tube were added the intermediate pyridine diamine derivative (226mg, 0.5 mmol), ammonium hexafluorophosphate (90mg, 1.1mmol), and triethyl orthoformate (1 mL). Heat at 120 ℃ overnight. After cooling to room temperature, ethyl acetate was added to precipitate a yellow precipitate, which was filtered to give carbene hexafluorophosphate (yellow solid, yield 60%).
Synthesis of complex 6:
the intermediates 1-5 (304mg, 0.5 mmo), dichloro (1,5-cyclooctadiene) platinum (II) (Pt (COD) Cl) were added to the tube 2 168mg, 0.45mmol), sodium acetate (43mg, 0.53mmol) and THF (1 mL). Heating at 120 deg.C for 3 days. After cooling to room temperature, spin-dry and purify the obtained solution by silica gel chromatography using DCM: PE = 2: 1 as eluent to obtain the target product: complex 6 (yellow powder, yield 70%). NMR (400MHz, CDCl) 3 )δ8.86(d,J＝5.6Hz,1H),8.29(d,J＝7.6Hz,1H),7.78-7.76(m,2H),7.69(d,J＝8.4Hz,1H),7.21-7.13(m,2H),7.11-7.07(m,3H),5.29-5.23(m,1H),3.14-3.09(m,1H),2.71(s,3H),1.65(d,J＝7.2Hz,6H),1.40(d,J＝7.2Hz,6H).MS(ESI):657.5[M] + The emission peak in Dichloromethane (DCM) solution was 562nm, full width at half maximum (FWHM) =69nm, the emission peak in Polymethylmethacrylate (PMMA) film was 561nm, FWHM =147nm.
EXAMPLE 2 Complex 15 and preparation thereof
Synthesis of pyridine diamine derivative 2-1:
addition of intermediate 3- ((6 '-isopropyl- [2,4' -bipyridine) to one sealed tube in glove box]-2' -yl) oxy) aniline (305mg, 1mmol), 2-chloro-N- (2,6-diisopropylphenyl) -6-methylpyridin-3-amine (332mg, 1.1mmol), tris (dibenzylideneacetone) dipalladium (45.5mg, 0.05 mmol), 1,1 '-binaphthyl-2,2' -bis-diphenylphosphine (31.1mg, 0.5 mmol), sodium tert-butoxide (144mg, 1.5 mmol) and toluene (4 mL). After bubbling the mixture for 15 minutes, the mixture was heated at 130 ℃ for 20 hours. After cooling, ethyl acetate was added, and the mixture was filtered. Extracting the aqueous phase with ethyl acetate, mixing the organic phases, washing with brine, and adding anhydrous Na 2 SO 4 And (5) drying. The obtained solution was purified by silica gel chromatography using PE: EA = 6: 1 as an eluent, and the eluent was spin-dried to obtain the pyridine diamine derivative 2-1 (yellow viscous liquid, yield 90%).
Synthesis of carbene hexafluorophosphate 2-2:
to one sealed tube were added the intermediate pyridyldiamine derivative (285mg, 0.5mmol), ammonium hexafluorophosphate (90mg, 1.1mmol), and triethyl orthoformate (1 mL). Heat at 120 ℃ overnight. After cooling to room temperature, ethyl acetate was added to precipitate a yellow precipitate, which was filtered to give carbene hexafluorophosphate 2-2 (yellow solid, yield 60%).
Synthesis of Complex 15:
the intermediate 2-2 (364mg, 0.5 mmo), dichloro (1,5-cyclooctadiene) platinum (II) (Pt (COD) Cl) were added to the sealed tube 2 168mg, 0.45mmol), sodium acetate (43mg, 0.53mmol) and THF (1 mL). Heating at 120 deg.C for 3 days. After cooling to room temperature, spin-dry and purify the obtained solution by silica gel chromatography using DCM: PE = 2: 1 as eluent to obtain the target product: complex 6 (yellow powder, yield 70%). NMR (400MHz, CDCl) 3 )δ8.84(dd,J＝7.2,1.6Hz,1H),7.83(d,J＝8.0Hz,1H),7.76(t,J＝8.0Hz,1H),7.72-7.68(m,1H),7.52(d,J＝8.0Hz,2H),7.39-7.32(m,2H),7.18(s,1H),7.16-7.10(m,2H),6.66(d,J＝5.6,1H),6.58-6.55(m,1H),3.16-3.12(m,1H),2.78(s,3H),2.70-2.63(m,2H),1.38(s,3H),1.36(s,3H),1.09(d,J＝6.8Hz,6H),1.05(d,J＝6.8Hz,6H)。MS(ESI):776.7[M+1] + . The peak value of luminescence in Dichloromethane (DCM) solution is 549nm, the full width at half maximum (FWHM) =59nm, the peak value of luminescence in polymethyl methacrylate (PMMA) film is 545nm, and the FWHM =35nm.
EXAMPLE 3 Complex 81 and preparation thereof
Synthesis of 2' - (3-nitrophenoxy) -6' -phenyl-2,4 ' -bipyridine:
to a 5mL stopcock equipped with a magnetic rotor was added 2' -chloro-6 ' - (3-nitrophenoxy) -2,4' -bipyridine (107.9 mg, 0.33mmol), phenylboronic acid (100mg, 0.825mmol), tetrakistriphenylphosphine palladium (12mg, 0.01mmol), potassium carbonate (69mg, 0.5mmol), ethylene glycol dimethyl ether (0.75 mL), and water (0.75 mL), and the resulting mixture was bubbled with nitrogen for 10 minutes, then heated to 100 ℃ and stirred overnight. Cooling to room temperature, adding water to quench the reaction, extracting with ethyl acetate, combining organic phases, washing with a proper amount of saturated sodium chloride aqueous solution, and then adding anhydrous sodium sulfate for drying. The solvent was removed by distillation under the reduced pressure, and the resulting crude product was isolated and purified by silica gel column chromatography with petroleum ether/ethyl acetate = 25: 1 as eluent to give a white solid with a yield of 98%.
3- ((6 '-phenyl- [2,4' -bipyridine)]-2' -yl) oxy) aniline synthesis:
to a 50mL round bottom flask with magnetic rotor, 2' - (3-nitrophenoxy) -6' - (prop-1-en-2-yl) -2,4' -bipyridine (120mg, 0.325mmol), pd/C (10 mg), methanol (8 mL) and tetrahydrofuran (8 mL) was stirred at room temperature under an atmosphere of hydrogen for 24 hours. After the reaction is finished, the reaction system is subjected to suction filtration treatment and washed by a large amount of ethyl acetate, the filtrate obtained by suction filtration is subjected to reduced pressure distillation to remove the solvent, the obtained crude product is separated and purified by silica gel column chromatography, and the eluent is petroleum ether and ethyl acetate = 25: 1, so that white solid is obtained, and the yield is 78%.
Synthesis of pyridine diamine derivative 3-3:
addition of intermediate 3- ((6 '-isopropyl- [2,4' -bipyridine) to one sealed tube in glove box]-2' -yl) oxy) aniline (339mg, 1mmol), 2-chloro-N-isopropyl-6-methylpyridin-3-amine (202mg, 1.1mmol), tris (dibenzylideneacetone) dipalladium (45.5mg, 0.05mmol), 1,1' -binaphthyl-2,2 ' -bis-diphenylphosphine (31.1mg, 0.5mmol), sodium tert-butoxide (144mg, 1.5mmol), and toluene (4 mL). After bubbling the mixture for 15 minutes, the mixture was heated at 130 ℃ for 20 hours. After cooling, ethyl acetate was added, and the mixture was filtered. Extracting the aqueous phase with ethyl acetate, mixing the organic phases, washing with brine, and adding anhydrous Na 2 SO 4 And (5) drying. The obtained solution was purified by silica gel chromatography using PE: EA = 6: 1 as an eluent, and the eluent was spin-dried to obtain pyridyldiamine derivative 3-3 (yellow viscous liquid, yield 90%).
Synthesis of carbene hexafluorophosphate 3-4:
to a sealed tube were added the intermediate pyridyldiamine derivative (243mg, 0.5mmol), ammonium hexafluorophosphate (90mg, 1.1mmol), and triethyl orthoformate (1 mL). Heat at 120 ℃ overnight. After cooling to room temperature, ethyl acetate was added to precipitate a yellow precipitate, which was filtered to give carbene hexafluorophosphate (yellow solid, yield 60%).
Synthesis of Complex 81:
the intermediate 3-4 (322mg, 0.5 mmo), dichloro (1,5-cyclooctadiene) platinum (II) (Pt (COD) Cl) was added to the tube 2 168mg, 0.45mmol), sodium acetate (43mg, 0.53mmol) and THF (1 mL). Heating at 120 deg.C for 3 days. After cooling to room temperature, spin-dry and purify the obtained solution by silica gel chromatography using DCM: PE = 2: 1 as eluent to obtain the target product: complex 81 (yellow powder, yield 70%). NMR (400MHz, CDCl) 3 )δ8.91(d,J＝5.2Hz,1H),8.38(d,J＝7.2,1H),8.15(d,J＝1.6Hz,1H),8.13-8.12(m,1H),7.87(d,J＝8.0Hz,1H),7.82-7.78(m,1H),7.73-7.71(m,1H),7.65(s,1H),7.52-7.47(m,3H),7.43-7.41(m,1H),7.23-7.18(m,2H),7.11-7.09(m,1H),5.35-7.28(m,1H),2.71(s,3H),1.70(d,J＝6.0Hz,6H).MS(ESI):690.6[M] + . The peak value of luminescence in Dichloromethane (DCM) solution is 567nm, full width at half maximum (FWHM) =61nm, the peak value of luminescence in polymethyl methacrylate (PMMA) film is 5631 nm, FWHM =70nm.
EXAMPLE 4 characterization of the luminescent Properties of complexes 6, 15 and 81
The above complexes 6, 15 and 81 are yellow phosphorescent light emitting materials or phosphorescent light emitting materials. The yellow phosphor wavelength peak value is in the range of 550-570 nm.
Representative data for emitter color purity can be obtained from the emission spectra of thin films prepared using 5% doped complex materials in Polymethylmethacrylate (PMMA). Table 1 shows the emission spectra of the individual complexes. In table 1 below, λ is a peak wavelength, and CIE (x, y) is a chromaticity coordinate parameter according to the international commission on illumination standard. The peak wavelengths of the complexes 6, 15 and 81 prepared by the embodiment of the invention are 545-570nm, the half-peak widths are more than 35nm, and the divalent platinum complex with the structure shown in the general formula I is a yellow phosphorescent luminescent material.
TABLE 1 emission spectra data of the complexes
FIGS. 1 to 3 show luminescence spectra of divalent platinum complexes 6, 15 and 81 in solution and in thin films, respectively, in sequence; under the excitation of 400nm ultraviolet light, the light emitting wavelengths of the three complexes in methylene chloride solution and polymethyl methacrylate (PMMA) are between 550 and 570nm, and all the complexes have the wavelength in a yellow phosphor region. Wherein, FIG. 1 shows the effect of co-luminescence of molecular monomers and aggregation states, which indicates that the series of divalent platinum complexes with 5-6-5 ring closure structures are good yellow luminescent materials with adjustable and controllable spectrum.
FIGS. 4 and 5 show the UV-VIS absorption spectra of the divalent platinum complexes 6 and 15 in methylene chloride solution, and it can be known from the absorption spectra that the absorption of the absorption spectra is very strong in the range of 250-450 nm. Wherein the absorption below 370nm can be assigned as the ligand-centered pi-pi in the complex * And (4) transition. Wherein the absorption peak after 370nm can be assigned as valence transition (MLCT) transition between the metal ion and the ligand at the center of the complex. The energy absorption of such molecules is very efficient and can be used as a preferred molecular structure of the doped material molecules. The wavelength below 280nm is pi-pi of benzene ring or pyridine ring under the permission of spin * Transition, 280nm-370nm being pi-pi of the carbazole ligand moiety * Transition; absorption at wavelengths above 370nm results from the transfer of the metal to the ligand state * And (4) transition.
The band gaps and related optical properties of the divalent platinum complexes 6, 15, 81 provided by embodiments of the present invention are characterized as follows: band gap value (E) of the material g ) The Lowest Unoccupied Molecular Orbital (LUMO) and Highest Occupied Molecular Orbital (HOMO) values were measured using Cyclic Voltammetry (CV). The whole test process is carried out on CHI600D electrochemical workstation (Shanghai Chenghua apparatus Co.) in glove box (Lab 2000, etelux), pt column is used as working electrode, ag/AgCl is used as reference electrode, pt wire is used as auxiliary electrode to form three-electrode system, and the medium adopted in the test process is 0.1M tetrabutylammonium hexafluorophosphate (Bu) 4 NPF 6 ) The potentials measured were all internal standards of ferrocene (Fc) added. In the following table, λ is the peak wavelength of the divalent platinum complex dissolved in dichloromethane, FWHM is the half-peak width thereof, and triplet photon energy (E) of the material T1 ) From the formula 1240/λ 0→1 By calculation of (lambda) 0→1 Is the first under 77K conditionVibration peak) in units of electron ford (eV).
TABLE 2 energy level data
| Complexes | E HOMO (eV) | E LUMO (eV) | E g (eV) | λ(nm) | E T1 (eV) |
| Complex 6 | -5.22 | -2.68 | 2.54 | 523 | 2.37 |
| Complex 15 | -5.56 | -2.64 | 2.92 | 514 | 2.41 |
| Complex 81 | -5.12 | -2.74 | 2.38 | 533 | 2.33 |
FIGS. 6 and 7 are monomolecular of complexes 6 and 15, respectively 1 H nuclear magnetic spectrum shows that the complex can exist independently and stably through hydrogen spectrum, and is easy to separate, purify and characterize. From the nuclear magnetic spectrum, the bivalent platinum complex does not show signals of aggregation morphology except that the bivalent platinum complex has stable structural representation, which indicates that the bivalent platinum complex molecules exist in a state of single molecule separation in a solution state.
FIG. 8 is an analysis diagram of the purity of complex 15 after purification in an ultra-high pressure liquid phase. The liquid phase purity is 99.1%, which illustrates the utility of the process provided by the present specification to obtain ultra-high purity products and the availability of the complex for suitable process scaling-up.
FIG. 9 is a mass spectrum characterization of the molecule of complex 15. The molecular signal of the mass spectrum molecule shows that the M/C peak value is 776.7, which is consistent with the molecular ion peak of the compound 15, and the structure of the complex is a designed structure.
FIG. 10 is a mass spectrum characterization of the molecule of complex 81. The molecular signal of the mass spectrum molecule shows that the M/C peak value is 690.6, which is consistent with the molecular ion peak of the compound 81, and the complex structure is a designed structure.
EXAMPLE 5 use of complexes 6, 15 and 81 in organic optoelectronic devices
The invention provides an organic photoelectric device which comprises a light-emitting layer, wherein a divalent platinum complex is a light-emitting material, a host material or a guest material in the light-emitting layer of the organic photoelectric device.
FIG. 11 shows a cross-sectional view of an OLED light emitting device 1000 that includes one of the divalent platinum complexes disclosed herein. OLED device 1000 includes a substrate 1002, an anode layer 1004, a hole transport layer 1006, a light emitting layer 1008, an electron transport layer 1010, and a metallic cathode layer 1012. The anode 1004 is typically a transparent material such as indium tin oxide. Light emitting layer 1008 can be a light emitting material that includes one or more emitters and a host. Where EIL refers to an electron injection layer, it can be considered as a part of the electron transport layer 1010. HIL is a hole injection layer and can be considered to be part of the hole transport layer 1006. CPL is the cathode capping layer.
And sequentially placing a crucible containing OLED organic materials and a crucible containing metal aluminum particles on an organic evaporation source and an inorganic evaporation source. And closing the cavity, and performing primary vacuum pumping and high vacuum pumping to ensure that the vacuum degree of evaporation in the OLED evaporation equipment reaches 10E-7Torr. An OLED evaporation film forming method comprises the following steps: and opening an OLED organic evaporation source, and preheating the OLED organic material at 100 ℃ for 15 minutes to ensure that water vapor in the OLED organic material is further removed. And then carrying out rapid heating treatment on the organic material to be evaporated, opening a baffle above an evaporation source until the organic material runs out of the evaporation source of the material, and slowly raising the temperature when a crystal oscillator piece detector detects the evaporation rate, wherein the temperature rise amplitude is 1-5 ℃, opening the baffle right below a mask plate until the evaporation rate is stabilized at 1A/s, carrying out OLED film formation, closing the baffle above the mask plate and the baffle right above the evaporation source when a computer end detects that the organic film on the ITO substrate reaches a preset film thickness, and closing an evaporation source heater of the organic material. The evaporation process for the other organic materials and the cathode metal material is as described above. And the packaging adopts UV epoxy resin for photocuring packaging. The encapsulated samples were tested for IVL performance using Mc Science M6100 for IVL equipment.
The complex 6, the complex 15 and the complex 81 disclosed in the specification are used as yellow phosphorescent light-emitting doping materials in a light-emitting layer, and a yellow phosphorescent device is prepared. When the complex doping material is used in an OLED device, a phosphorescence device is prepared by a distillation method, and the structure of the device 1 is (ITO, 95 nm)/4,4 '-cyclohexyl bis [ N, N-bis (4-methylphenyl) aniline ] (TAPC, 30 nm)/9,9' - (1,3-phenyl) di-9H-carbazole (mCP, 10 nm)/mCP: complex (20, 20 nm)/bis [2- ((oxo) diphenylphosphino) phenyl ] ether (DPEPO, 5 nm)/3,3 '- [5' - [3- (3-pyridyl) phenyl ] [1,1':3',1 '-terphenyl ] -3,3' -diyl ] bipyridine (TmPyPB, 40 nm)/lithium fluoride (LiF, 1 nm)/aluminum (Al, 100 nm),
wherein ITO is an anode, TAPC is a hole transport material layer 1, mCP is a hole transport layer 2 and a luminescent layer main body material, DPEPO and TmPyPB are electron transport layers, and Al is a cathode. Wherein the electroluminescence spectrum is shown in FIG. 12:
the yellow phosphorus light device prepared by the complex 15 has the peak wavelength of 560nm and the half-peak width of 50nm, the yellow phosphorus light device prepared by the complex 81 has the peak wavelength of 576nm and the half-peak width of 72nm, the yellow phosphorus light device prepared by the complex 6 has the peak wavelength of 573nm and the half-peak width of 180nm, and EL light shows that the yellow phosphorescent material contained in the light-emitting device can realize spectrum adjustment through molecular design, wherein the CIE coordinate of an electronic light emission spectrum is shown in figure 13. Wherein the complex 15 is used for preparing CIE coordinates (0.43,0.57) of an electronic luminescence spectrum of a device; CIE coordinates of the electroluminescence spectrum of the device prepared from complex 81 (0.46,0.53); the CIE coordinate of the electron luminescence spectrum of the device prepared from the complex 6 is (0.50,0.49), and the CIE of the device is in a yellow region. It is fully described that the spectral tunability in the yellow region can be satisfied by designing the material provided by the present invention.
In the structure of the OLED light emitting device 1000, the light emitting layer 1008 may include one or more divalent platinum complexes provided by the present invention, optionally together with a host material and one or more dopant materials. This specification provides a novel device structure as follows:
ITO/HIL (10 nm)/HTL (70 nm)/EML (20 nm)/HBL (10 nm)/ETL (40 nm)/EIL (2 nm)/Al, wherein HIL is a hole injection layer which can be HATCN; HTL is that the hole transport layer may be TAPC; NPD; PT301; the EML is a light-emitting layer, the platinum complex is doped with a host material, the doping proportion can be 1-10%, and the host material can be mCP;2,6mCPy, mCBP; HBL is a hole blocking layer and can be 2,6mcpy; ETL is an electron transport layer and can be TPBi, DPPS, BPyTP, and the like.
Wherein HATCN is 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene; NPD is N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4,4' -diamine; PT-301 is 4,4 '-bis [ N, N-bis (biphenyl-4-yl) amino ] -1,1' -biphenyl; 2,6mCPY is 2,6-Di (9H-carbazol-9-yl) pyridine; mCBP is 3,3 '-bis (9H-carbazol-9-yl) -1,1' -biphenyl; TPBi is 1,3,5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene; DPPS is diphenylbis [4- (pyridin-3-yl) phenyl ] silane; BPyTP is 2,7-bis (2,2' -bipyridin-5-yl) triphenylene
The efficiency of devices made with the materials of the present invention is shown in figure 14.
As can be seen from fig. 14, the device prepared using the material of the present invention has excellent photoelectric properties. Wherein the maximum EQE of the device prepared from the complex 81 is 13.5%, the maximum EQE of the device prepared from the complex 15 is 18%, and the maximum EQE of the device prepared from the complex 6 is 11.8%. The yellow phosphorescent material provided by the invention is suitable for preparing a high-efficiency yellow phosphorescent device.
Three exemplary complexes were used to prepare yellow phosphorescent devices with the above device structures, and the device results are shown in table 3.
TABLE 3 luminescent Properties of the devices
Table 3 shows the comparison of the luminescence property data of the white phosphor light emitting device prepared from each complex. Under the same condition, the efficiency of the light-emitting device is consistent with the luminous quantum efficiency of the platinum complex per se and is 1000 cd.m -2 The efficiency is higher under the brightness. The spectrum of the light emitting device is substantially consistent with the luminescence of the yellow phosphorescent material.
The invention is demonstrated by an exemplary example that the general structural formula I can be used as a yellow phosphor doping material to prepare a single doping Huang Linguang device and form a double doping white phosphor device with a blue phosphor doping material, wherein the materials are not limited to the exemplary structures; depending on the application, the device structure may be either a bottom emitting device or a top emitting device. Wherein the ETL layer 1010 and the HTL 1006 may further comprise one or more transport layer materials, and there may be another charge injection layer in the divalent platinum complex and in proximity to the electrode. The materials of the injection layer may include EIL (electron injection layer), HIL (hole injection layer) and CPL (cathode capping layer), which may be in the form of a single layer or dispersed in an electron or hole transport material. The host material may be any suitable host material known in the art. The emission color of the OLED is determined by the emission energy (optical energy gap) of the material of the light-emitting layer 1008, which can be tuned by tuning the electronic structure of the emitting divalent platinum complex and/or host material as described above. The hole transport material in the HTL layer 1006 and the electron transport material in the ETL layer 1010 may include any suitable hole transporter known in the art. The divalent platinum complex provided by the embodiment of the invention can exhibit phosphorescence. Phosphorescent OLEDs (i.e., OLEDs having phosphorescent emitters) generally have higher device efficiencies than other OLEDs, such as fluorescent OLEDs.
The foregoing shows and describes the general principles, principal features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. A divalent platinum complex having the structure of formula I:
wherein R is a 、R c And R d Each independently is a mono-or di-substituent, and R a 、R c And R d Each independently selected from a single atom substituent or a multiple atom substituent; r b 、R e Are substituents each independently containing at least 1 carbon atom; the monoatomic substituent includes a hydrogen atom, an isotope atom thereof, or a halogen atom; the polyatomic substituent is an alkyl or aryl substituent with 1 to 14 carbon atoms and comprisesAlkyl, aryl-substituted alkyl, fluoro-substituted alkyl, aryl, alkyl-substituted aryl, aryl-substituted aryl, or the above-mentioned substituents containing an isotopic atom.
2. The divalent platinum complex according to claim 1, wherein R is a 、R c And R d May be each independently selected from a hydrogen atom, a deuterium atom, a fluorine atom; r a 、R b 、R c 、R d 、R e Selected from deuterated or non-deuterated methyl, benzyl, diphenylmethyl, triphenylmethyl; ethyl, 2-phenylethyl, 2,2-phenylethyl, 2,2,2-trifluoroethyl; propyl, isopropyl, 3,3,3-trifluoropropyl, 1,1,1,3,3,3-hexafluoro-2-propyl; n-butyl, isobutyl, hexafluoroisobutyl, tert-butyl; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl; phenyl, 2-methylphenyl, 2-isopropylphenyl, 2-ethylphenyl, 4-methylphenyl, 4-isopropylphenyl, 4-ethylphenyl, 4-tert-butylphenyl, -dimethylphenyl, -diethylphenyl, -diisopropylphenyl, -diisobutylphenyl, -dicyclohexylphenyl, -dicyclopropylphenyl, -dicyclobutylphenyl, -dicyclopentylphenyl, -dimethylphenyl, -diethylphenyl, -diisopropylphenyl, -diisobutylphenyl, -dicyclohexylphenyl, -dicyclopropylphenyl, -dicyclopentylphenyl, -dimethylphenyl, di-ethylphenyl, 4-isopropylphenyl, 4-ethylphenyl, 4-tert-butylphenyl, di-ethylphenyl, -diethylphenyl, -diisopropylphenyl, -dicyclopentylphenyl-diethylphenyl, -diisopropylphenyl, -diisobutylphenyl, -dicyclohexylphenyl, -dicyclopropylphenyl, -dicyclobutylphenyl, -dicyclopentylphenyl, -dimethylphenyl, -diethylphenyl, -diisopropylphenyl, -diisobutylphenyl, -dicyclohexylphenyl, -dicyclopropylphenyl, -dicyclopentylphenyl, -tetramethylphenyl, -trimethylphenyl, -triethylphenyl, -triisopropylphenyl, -triisobutylphenyl, -tricyclohexylphenyl, -tricyclopropylphenyl, -tricyclopentylphenyl.
3. The divalent platinum complex according to claim 1, wherein the divalent platinum complex has a structure selected from one of the following complexes 1 to 90:
4. the divalent platinum complex according to claim 1, wherein R in the divalent platinum complex is a 、R c And R e Is a hydrogen atom, R e Selected from alkyl and aryl; r a 、R c And R d Is a hydrogen atom, R b Selected from alkyl and aryl groups.
5. A process for the preparation of a divalent platinum complex according to any one of claims 1 to 4, comprising the following synthetic steps:
the first step is as follows: through 4-R a Substituted pyridyl-2,6-dichloro, bromo, iodo or triflate substituted pyridines are the basic units to which they are coupled;
the second step is that: carrying out two coupling reactions to respectively obtain intermediates coupled with corresponding fragments, wherein the two coupling reactions comprise any one of Ullmann coupling, buchwald-hartwig coupling reaction or similar coupling reaction;
the third step: imidazole ring closure reaction, specifically, under the action of a fluorine-containing anion salt, performing one-step condensation cyclization of a coupled intermediate and trialkyl orthoformate to obtain a precursor of a final product ligand, wherein the fluorine-containing anion of the precursor comprises hexafluorophosphate negative ions, tetrafluoroborate negative ions, trifluoromethanesulfonic acid negative ions or trifluoromethanesulfonimide negative ions;
the fourth step: divalent platinum complex synthesis, wherein the ligand precursor and a divalent platinum compound are reacted at the temperature of more than 80 ℃ to directly obtain the divalent platinum complex, wherein the divalent platinum compound can be potassium tetrachloroplatinate, (1,5-cyclooctadiene) platinum dichloride, platinum dichloride and the like.
6. A method for preparing the complex 6 as claimed in claim 3, which comprises the following steps:
the first step is as follows:synthesis of 2' -chloro-6 ' - (3-nitrophenoxy) -2,4' -bipyridine:
2',6' -dichloro-2,4 ' -bipyridine (1.37g, 4.4 mmol), 3-nitrophenol (0.56g, 4 mmol), 2,2,6,6-tetramethyl-3,5-heptanedione (590mg, 3.2mmol), cuprous bromide (58mg, 0.4 mmol), cesium carbonate (3.26g, 10mmol), and N, N-dimethylformamide (20 mL) were added to a 75mL sealed tube with a magnetic rotor, and the resulting mixture was heated to 130 ℃ after bubbling with nitrogen for 10 minutes, stirred for 36 hours, cooled to room temperature, quenched with water, extracted with ethyl acetate, the organic phase was combined, washed with an appropriate amount of saturated aqueous sodium chloride solution and then dried with anhydrous sodium sulfate, the solvent was removed by distillation under reduced pressure, the resulting crude product was separated and purified by silica gel column chromatography, and the eluent petroleum ether: ethyl acetate = 25: 1, to give a white solid with a yield of 46%;
the second step is that: synthesis of 2' - (3-nitrophenoxy) -6' - (prop-1-en-2-yl) -2,4' -bipyridine:
adding 2' -chloro-6 ' - (3-nitrophenoxy) -2,4' -bipyridine (107.9 mg, 0.33mmol), 4,4,5,5-tetramethyl-2- (prop-1-en-2-yl) -1,3,2-dioxaborane (139mg, 0.825mmol), tetratriphenylphosphine palladium (12mg, 0.01mmol), potassium carbonate (69mg, 0.5mmol), ethylene glycol dimethyl ether (0.75 mL) and water (0.75 mL) to a 5mL lock tube with a magnetic rotor, heating the resulting mixture to 100 ℃ after bubbling with nitrogen for 10 minutes, stirring overnight with stirring, cooling to room temperature, adding water to quench the reaction, extracting with ethyl acetate, combining the organic phases, washing with an appropriate amount of saturated aqueous solution of chloride, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove the solvent, separating and purifying the resulting crude product by silica gel column chromatography with the petroleum ether: ethyl acetate = 25: 1 to obtain a white solid with a yield of 98%;
the third step: 3- ((6 '-isopropyl- [2,4' -bipyridine)]-2' -yl) oxy)) aniline synthesis:
to a 50mL round bottom flask with a magnetic rotor, 2' - (3-nitrophenoxy) -6' - (prop-1-en-2-yl) -2,4' -bipyridine (108mg, 0.325mmol), pd/C (10 mg), methanol (8 mL) and tetrahydrofuran (8 mL), the resulting mixture was stirred at room temperature for 24 hours under a hydrogen atmosphere, after completion of the reaction, the reaction system was subjected to suction filtration and washed with a large amount of ethyl acetate, the filtrate obtained by suction filtration was subjected to distillation under reduced pressure to remove the solvent, and the resulting crude product was subjected to separation and purification by silica gel column chromatography with an eluent of petroleum ether: ethyl acetate = 25: 1 to obtain a white solid in 78% yield;
the fourth step: synthesis of pyridine diamine derivatives 1 to 4:
addition of intermediate 3- ((6 '-isopropyl- [2,4' -bipyridine) to one sealed tube in glove box]-2' -yl) oxy) aniline (305mg, 1mmol), 2-chloro-N-isopropyl-6-methylpyridin-3-amine (202mg, 1.1mmol), tris (dibenzylideneacetone) dipalladium (45.5mg, 0.05mmol), 1,1' -binaphthyl-2,2 ' -bis-diphenylphosphine (31.1mg, 0.5mmol), sodium tert-butoxide (144mg, 1.5mmol) and toluene (4 mL), after bubbling the mixture for 15 minutes, the mixture was heated at 130 ℃ for 20 hours, after cooling, ethyl acetate was added, and then the mixture was filtered. Extracting the aqueous phase with ethyl acetate, mixing the organic phases, washing with brine, and adding anhydrous Na 2 SO 4 Drying, purifying the obtained solution by silica gel chromatography using PE: EA = 6: 1 as an eluent, and spin-drying the eluent to obtain the pyridine diamine derivative 1-4 (yellow viscous liquid, yield 90%);
the fifth step: synthesis of carbene hexafluorophosphate 1-5:
adding intermediate pyridine diamine derivative (226mg, 0.5 mmol), ammonium hexafluorophosphate (90mg, 1.1mmol) and triethyl orthoformate (1 mL) into a sealed tube, heating at 120 ℃ overnight, cooling to room temperature, adding ethyl acetate to precipitate a yellow precipitate, and filtering to obtain carbene hexafluorophosphate (yellow solid, yield 60%);
and a sixth step: synthesis of complex 6:
adding intermediate 1-5 (304mg, 0.5 mmo), dichloro (1,5-cyclooctadiene) platinum (II) (Pt (COD) Cl) into a sealed tube 2 168mg, 0.45mmol), sodium acetate (43mg, 0.53mmol) and THF (1 mL), heated at 120 ℃ for 3 days, cooled to room temperature and spun dry, and the resulting solution was purified by silica gel chromatography using DCM: PE = 2: 1 as eluent to give the desired product: complex 6 (yellow powder, yield 70%).
7. A method for preparing the complex 15 as claimed in claim 3, comprising the following steps:
the first step is as follows: synthesis of pyridine diamine derivative 2-1:
addition of intermediate 3- ((6 '-isopropyl- [2,4' -bipyridine) to one sealed tube in glove box]-2' -yl) oxy) aniline (305mg, 1mmol), 2-chloro-N- (2,6-diisopropylphenyl) -6-methylpyridin-3-amine (332mg, 1.1mmol), tris (dibenzylideneacetone) dipalladium (45.5mg, 0.05mmol), 1,1' -binaphthyl-2,2 ' -bis-diphenylphosphine (31.1mg, 0.5mmol), sodium tert-butoxide (144mg, 1.5mmol) and toluene (4 mL), after bubbling the mixture for 15 minutes, the mixture is heated at 130 ℃ for 20 hours, after cooling, ethyl acetate is added, then the mixture is filtered, the aqueous phase is extracted with ethyl acetate and the organic phases are mixed, washed with brine, washed with anhydrous Na 2 SO 4 And (5) drying. Purifying the obtained solution by silica gel chromatography with PE: EA = 6: 1 as eluent, and spin-drying the eluent to obtain the pyridine diamine derivative 2-1 (yellow viscous liquid, yield 90%);
the second step is that: synthesis of carbene hexafluorophosphate 2-2:
adding an intermediate pyridine diamine derivative (285mg, 0.5mmol), ammonium hexafluorophosphate (90mg, 1.1mmol) and triethyl orthoformate (1 mL) into a sealed tube, heating at 120 ℃ overnight for cooling, adding ethyl acetate to precipitate yellow precipitate after cooling to room temperature, and filtering to obtain carbene hexafluorophosphate 2-2 (yellow solid, yield 60%);
the third step: synthesis of complex 15:
the intermediate 2-2 (364mg, 0.5 mmo), dichloro (1,5-cyclooctadiene) platinum (II) (Pt (COD) Cl) were added to the sealed tube 2 168mg, 0.45mmol), sodium acetate (43mg, 0.53mmol) and THF (1 mL), heated at 120 ℃ for 3 days, cooled to room temperature and spun dry, and the resulting solution was purified by silica gel chromatography using DCM: PE = 2: 1 as eluent to give the desired product: complex 6 (yellow powder, yield 70%).
8. A method for preparing the complex 81 according to claim 3, comprising the following steps:
the first step is as follows: synthesis of 2' - (3-nitrophenoxy) -6' -phenyl-2,4 ' -bipyridine:
adding 2' -chloro-6 ' - (3-nitrophenoxy) -2,4' -bipyridine (107.9 mg, 0.33mmol), phenylboronic acid (100mg, 0.825mmol), tetratriphenylphosphonium palladium (12mg, 0.01mmol), potassium carbonate (69mg, 0.5mmol), ethylene glycol dimethyl ether (0.75 mL) and water (0.75 mL) into a 5mL sealed tube with a magnetic rotor, bubbling the obtained mixture with nitrogen for 10 minutes, heating to 100 ℃, stirring overnight, cooling to room temperature, adding water to quench the reaction, extracting with ethyl acetate, combining the organic phases, washing with an appropriate amount of saturated sodium chloride aqueous solution, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove the solvent, separating and purifying the obtained crude product by silica gel column chromatography, wherein the eluent is petroleum ether: ethyl acetate = 25: 1 to obtain a white solid with a yield of 98%;
the second step is that: 3- ((6 '-phenyl- [2,4' -bipyridine)]-2' -yl) oxy) aniline synthesis:
to a 50mL round bottom flask with a magnetic rotor, 2' - (3-nitrophenoxy) -6' - (prop-1-en-2-yl) -2,4' -bipyridine (120mg, 0.325mmol), pd/C (10 mg), methanol (8 mL) and tetrahydrofuran (8 mL), the resulting mixture was stirred at room temperature for 24 hours under a hydrogen atmosphere, after completion of the reaction, the reaction system was subjected to suction filtration and washed with a large amount of ethyl acetate, the filtrate obtained by suction filtration was subjected to distillation under reduced pressure to remove the solvent, and the resulting crude product was subjected to separation and purification by silica gel column chromatography with an eluent of petroleum ether: ethyl acetate = 25: 1 to obtain a white solid in 78% yield;
the third step: synthesis of pyridine diamine derivative 3-3:
addition of intermediate 3- ((6 '-isopropyl- [2,4' -bipyridine) to one sealed tube in glove box]-2' -yl) oxy) aniline (339mg, 1mmol), 2-chloro-N-isopropyl-6-methylpyridin-3-amine (202mg, 1.1mmol), tris (dibenzylideneacetone) dipalladium (45.5mg, 0.05mmol), 1,1' -binaphthyl-2,2 ' -bis-diphenylphosphine (31.1mg, 0.5mmol), sodium tert-butoxide (144mg, 1.5mmol) and toluene (4 mL), after bubbling the mixture for 15 minutes, the mixture is heated at 130 ℃ for 20 hours, after cooling, ethyl acetate is added, then the mixture is filtered, the aqueous phase is extracted with ethyl acetate and the organic phases are mixed, washed with brineUsing anhydrous Na 2 SO 4 Drying, purifying the obtained solution by silica gel chromatography using PE: EA = 6: 1 as an eluent, and spin-drying the eluent to obtain the pyridine diamine derivative 3-3 (yellow viscous liquid, yield 90%);
the fourth step: synthesis of carbene hexafluorophosphate 3-4:
adding an intermediate pyridyldiamine derivative (243mg, 0.5mmol), ammonium hexafluorophosphate (90mg, 1.1mmol) and triethyl orthoformate (1 mL) to a sealed tube, heating at 120 ℃ overnight, cooling to room temperature, adding ethyl acetate to precipitate a yellow precipitate, and filtering to obtain carbene hexafluorophosphate (yellow solid, yield 60%);
the fifth step: synthesis of Complex 81:
the intermediate 3-4 (322mg, 0.5 mmo), dichloro (1,5-cyclooctadiene) platinum (II) (Pt (COD) Cl) was added to the tube 2 168mg, 0.45mmol), sodium acetate (43mg, 0.53mmol) and THF (1 mL). Heating at 120 ℃ for 3 days, cooling to room temperature and spin-drying, the solution obtained is purified by silica gel chromatography using DCM: PE = 2: 1 as eluent to give the desired product: complex 81 (yellow powder, yield 70%).
9. Use of a divalent platinum complex according to any one of claims 1 to 4 as an electroluminescent or photoluminescent material, preferably as a yellow-phosphorescent or phosphorescent light-emitting material in an organic optoelectronic device.
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