CN114716479A - Phosphine oxide compound with thermal activation delayed fluorescence property and preparation and application thereof - Google Patents
Phosphine oxide compound with thermal activation delayed fluorescence property and preparation and application thereof Download PDFInfo
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- CN114716479A CN114716479A CN202210490183.4A CN202210490183A CN114716479A CN 114716479 A CN114716479 A CN 114716479A CN 202210490183 A CN202210490183 A CN 202210490183A CN 114716479 A CN114716479 A CN 114716479A
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- Prior art keywords
- phosphine oxide
- oxide compound
- delayed fluorescence
- fluorescence property
- activated delayed
- Prior art date
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- -1 Phosphine oxide compound Chemical class 0.000 title claims abstract description 54
- 230000003111 delayed effect Effects 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000007725 thermal activation Methods 0.000 title abstract description 4
- 239000000463 material Substances 0.000 claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 37
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 28
- 239000003960 organic solvent Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- VLRYPRKTXDPVNN-UHFFFAOYSA-N 1,4-dibromo-2-iodobenzene Chemical compound BrC1=CC=C(Br)C(I)=C1 VLRYPRKTXDPVNN-UHFFFAOYSA-N 0.000 claims description 9
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 9
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 9
- IMDXZWRLUZPMDH-UHFFFAOYSA-N dichlorophenylphosphine Chemical compound ClP(Cl)C1=CC=CC=C1 IMDXZWRLUZPMDH-UHFFFAOYSA-N 0.000 claims description 8
- ZOBGVYXGBLDHHY-UHFFFAOYSA-L [Cl-].[Mg+2].C(C)(C)[Li].[Cl-] Chemical compound [Cl-].[Mg+2].C(C)(C)[Li].[Cl-] ZOBGVYXGBLDHHY-UHFFFAOYSA-L 0.000 claims description 7
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 7
- 229940071870 hydroiodic acid Drugs 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- LJPCNSSTRWGCMZ-UHFFFAOYSA-N 3-methyloxolane Chemical compound CC1CCOC1 LJPCNSSTRWGCMZ-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- VIJYEGDOKCKUOL-UHFFFAOYSA-N 9-phenylcarbazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2C2=CC=CC=C21 VIJYEGDOKCKUOL-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 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 3
- JXASPPWQHFOWPL-UHFFFAOYSA-N Tamarixin Natural products C1=C(O)C(OC)=CC=C1C1=C(OC2C(C(O)C(O)C(CO)O2)O)C(=O)C2=C(O)C=C(O)C=C2O1 JXASPPWQHFOWPL-UHFFFAOYSA-N 0.000 claims description 2
- BBXYLNWQWQDMIL-UHFFFAOYSA-N [Li]C(C)C.Cl Chemical compound [Li]C(C)C.Cl BBXYLNWQWQDMIL-UHFFFAOYSA-N 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
- 230000005693 optoelectronics Effects 0.000 claims 1
- YZWAZYXEBVGBNE-UHFFFAOYSA-N phenylphosphanium dichloride Chemical compound [Cl-].[Cl-].C1(=CC=CC=C1)[PH3+].C1(=CC=CC=C1)[PH3+] YZWAZYXEBVGBNE-UHFFFAOYSA-N 0.000 claims 1
- 238000006862 quantum yield reaction Methods 0.000 abstract description 10
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 abstract description 2
- 239000000370 acceptor Substances 0.000 abstract 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 45
- 239000000047 product Substances 0.000 description 31
- 239000000243 solution Substances 0.000 description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 239000003208 petroleum Substances 0.000 description 13
- 238000002189 fluorescence spectrum Methods 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 238000004440 column chromatography Methods 0.000 description 11
- 238000001035 drying Methods 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- 239000012044 organic layer Substances 0.000 description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- 239000003480 eluent Substances 0.000 description 8
- 238000000862 absorption spectrum Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000010409 thin film Substances 0.000 description 7
- 230000005284 excitation Effects 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- 230000001052 transient effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000001419 dependent effect Effects 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 239000008204 material by function Substances 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- JGAVTCVHDMOQTJ-UHFFFAOYSA-N (4-carbazol-9-ylphenyl)boronic acid Chemical compound C1=CC(B(O)O)=CC=C1N1C2=CC=CC=C2C2=CC=CC=C21 JGAVTCVHDMOQTJ-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000013058 crude material Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000003818 flash chromatography Methods 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 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
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical class [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- AKYHKWQPZHDOBW-UHFFFAOYSA-N (5-ethenyl-1-azabicyclo[2.2.2]octan-7-yl)-(6-methoxyquinolin-4-yl)methanol Chemical compound OS(O)(=O)=O.C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 AKYHKWQPZHDOBW-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000001576 FEMA 2977 Substances 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- TWWQCBRELPOMER-UHFFFAOYSA-N [4-(n-phenylanilino)phenyl]boronic acid Chemical group C1=CC(B(O)O)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 TWWQCBRELPOMER-UHFFFAOYSA-N 0.000 description 1
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- LOUPRKONTZGTKE-UHFFFAOYSA-N cinchonine Natural products C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229960003110 quinine sulfate Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000007619 statistical method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 239000013598 vector Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
- C07F9/65685—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms the ring phosphorus atom being part of a phosphine oxide or thioxide
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms
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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
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
- Y02B20/30—Semiconductor lamps, e.g. solid state lamps [SSL] light emitting diodes [LED] or organic LED [OLED]
Abstract
The invention provides a phosphine oxide compound with thermal activation delayed fluorescence property, and preparation and application thereof, wherein the structural formula of the phosphine oxide compound is as follows:
r is
Or
The compound takes phosphine oxide and carbonyl as acceptors, and a charge transfer state compound with a donor-acceptor structure is constructed by introducing a specific electron donor group into the acceptors, so that the size of the acceptors is reducedThe phosphine-oxygen compound has better luminous intensity, thermal stability and fluorescence quantum yield, provides a new choice for preparing devices with high luminous efficiency, and is suitable for preparing luminescent materials and photoelectric luminescent devices, and belongs to the technical field of luminescent materials.
Description
Technical Field
The invention belongs to the technical field of luminescent materials. More particularly, relates to a phosphine oxide compound and preparation and application thereof.
Background
Organic light-emitting diodes (OLEDs for short) have the advantages of self-luminescence, fast response, wide visibility, low driving voltage, energy saving, lightness and thinness, flexible processing and the like, and greatly meet the requirement of consumers on continuous update of display technology. Meanwhile, the OLED has wide application prospect and huge market demand in the field of illumination.
Organic electroluminescent elements (organic EL elements) can be classified into two types, i.e., fluorescent type and phosphorescent type, according to the principle of light emission. When a voltage is applied to the organic EL element, holes from the anode and electrons from the cathode are injected, and they are recombined in the light-emitting layer to form excitons. According to the electron spin statistical method, singlet excitons and triplet excitons are generated in a ratio of 25% to 75%. The fluorescent type uses singlet excitons to emit light, and thus its internal quantum efficiency can only reach 25%. A Thermally Active Delayed Fluorescence (TADF) material is a third generation organic light emitting material developed after organic fluorescent materials and organic phosphorescent materials. The kind materialThe material generally has a small singlet-triplet energy level difference (E)st) The triplet excitons can be converted into singlet excitons through reverse gap crossing to emit light, the singlet excitons and the triplet excitons formed under electric excitation can be fully utilized, the internal quantum efficiency of the device can reach 100%, and meanwhile, the material has controllable structure, stable property, low price, no need of precious metal and wide application prospect in the field of OLEDs.
In order to prepare a high-performance OLED light-emitting device, a high-performance OLED functional material needs to be selected and used, and for OLED functional materials with different functions, the basic requirements needed to be met are as follows:
1. the material has good thermal stability, namely, the material can not be decomposed in the long-time evaporation process, and meanwhile, the material is required to have good process reproducibility;
2. the OLED light-emitting device manufactured by matching with the OLED functional material has good performance, namely, better efficiency, longer service life and lower voltage are required. This requires materials with appropriate highest molecular occupied orbitals, lowest molecular unoccupied orbitals (HOMO, LUMO), and appropriate triplet energies.
In recent years, although the development of OLED functional materials has made some breakthrough, as lighting or display applications, there is a need to develop and innovate materials with better performance, especially organic functional materials with higher efficiency and better performance that can be applied to TADF systems.
Disclosure of Invention
In view of the above object, the present invention is directed to a phosphine oxide compound; the compound has better luminous intensity, thermal stability and fluorescence quantum yield, provides a new choice for preparing devices with high luminous efficiency, and is suitable for preparing luminescent materials and photoelectric luminescent devices.
The second object of the present invention is to provide a process for producing the above phosphine oxide compound.
The third purpose of the invention is to provide the application of the phosphine oxide compound in preparing luminescent materials or photoelectric luminescent devices.
It is a fourth object of the present invention to provide a luminescent material.
It is a fifth object of the present invention to provide a photovoltaic light emitting device.
To achieve the above object, a first aspect of the present invention is:
the invention provides a phosphine oxide compound with a thermal activation delayed fluorescence property, which has the following structural formula:
r is
Or alternatively
Specifically, the phosphine oxide compound has a chemical structure shown as the following formula (I) or formula (II):
the second technical object of the present invention is to provide a method for preparing the above phosphine oxide compound, comprising the steps of:
s1: dissolving 1, 4-dibromo-2-iodobenzene in an organic solvent, adding isopropyl lithium chloride magnesium chloride at the temperature of-15 ℃ under inert gas, stirring for 2 hours, and dropwise adding ethyl formate to obtain an intermediate 1;
s2: dissolving the intermediate 1 in an organic solvent, dropwise adding hydroiodic acid at normal temperature, and heating to react to obtain an intermediate 2;
s3: sequentially adding n-butyl lithium and phenyl phosphorus dichloride into the intermediate 1 obtained in the step S2 at the temperature of-80 to-70 ℃ in an organic solvent for reaction, stirring for 12-16 h, and adding hydrogen peroxide for reaction to obtain an intermediate 3;
s4: carrying out Suzuki reaction on the intermediate 3 and a donor group, dissolving the obtained mixture in an organic solvent, adding DDQ at 0 ℃, and stirring at room temperature for 10 hours to obtain the phosphine oxide compound;
wherein the donor group is 9-phenyl-9H-carbazole or triphenylamine.
Preferably, the molar ratio of the 1, 4-dibromo-2-iodobenzene, the isopropyl lithium chloride, the magnesium chloride and the ethyl formate in the step S1 is as follows: 1: 1 to 1.2: 0.5 to 0.7.
Most preferably, the molar ratio of the 1, 4-dibromo-2-iodobenzene to the isopropyl lithium chloride magnesium chloride to the ethyl formate is: 1: 0.5.
Preferably, the molar ratio of the intermediate 1 to the hydroiodic acid in step S2 is: 1: 2-2.5.
Most preferably, the molar ratio of the intermediate 1 to the hydroiodic acid in step S2 is: 1: 2.4.
Preferably, the molar ratio of the intermediate 1, n-butyllithium, phenylphosphorus dichloride and hydrogen peroxide in the step S3 is 1: 2.0-2.3: 1-2: 3-4.
Most preferably, in step S3, the molar ratio of the intermediate 1, n-butyl lithium, phenyl phosphorus dichloride and hydrogen peroxide is: 1: 2.2: 1.5: 3.5.
Preferably, the molar ratio of the mixture obtained in step S4 to DDQ is: 1: 2-2.5.
Most preferably, the molar ratio of the mixture obtained in step S4 to DDQ is: 1: 2.4.
Preferably, the organic solvent in step S1 is tetrahydrofuran or 4-methyltetrahydrofuran. Tetrahydrofuran is most preferred.
Preferably, the organic solvent in step S2 is acetic acid or formic acid. Most preferred is acetic acid.
Preferably, the organic solvent in step S3 is tetrahydrofuran, diethyl ether or toluene. Tetrahydrofuran is most preferred.
Preferably, the organic solvent in step S4 is methanol or ethanol. Most preferred is methanol.
Preferably, step S1 is specifically: dissolving 1, 4-dibromo-2-iodobenzene in an organic solvent, adding isopropyl lithium chloride magnesium chloride at the temperature of-15-20 ℃, stirring for 2-3 h, and dropwise adding ethyl formate to obtain an intermediate 1.
Most preferably, step S1 specifically includes: dissolving 1, 4-dibromo-2-iodobenzene in an organic solvent, adding isopropyl lithium chloride magnesium chloride at the temperature of-15 ℃, stirring for 2 hours, and dropwise adding ethyl formate to obtain an intermediate 1.
Preferably, the heating temperature in the step S2 is 120-130 ℃, and the time is 2-3 h.
Preferably, the heating temperature in step S2 is 130 ℃ and the time is 3 h.
Preferably, step S3 is specifically: and (4) dropwise adding n-butyllithium into the intermediate 1 obtained in the step S2 at the temperature of-80 to-70 ℃ in an organic solvent for reaction for 1-1.5 h, adding phenylphosphorus dichloride for reaction for 20-30 min, stirring for 12-16 h at the temperature of 20-30 ℃, and finally adding hydrogen peroxide and stirring for 2-4 h to obtain an intermediate 2.
Most preferably, step S3 is specifically: and (3) dropwise adding n-butyllithium into the intermediate 1 obtained in the step (S2) at the temperature of-78 ℃ in ether or tetrahydrofuran for reacting for 1h, then adding phenylphosphorus dichloride for reacting for 20min, stirring for 12h at the temperature of 25 ℃, and finally adding hydrogen peroxide and stirring for 2h to obtain an intermediate 2.
Preferably, step S4 is specifically: and (3) performing Suzuki reaction on the intermediate 3 and the donor group, dissolving the obtained mixture in an organic solvent, adding DDQ at the temperature of-5-0 ℃, and stirring at room temperature for 10-15 hours to obtain the phosphine oxide compound.
Most preferably, step S4 is specifically: and (3) carrying out Suzuki reaction on the intermediate 3 and a donor group, dissolving the obtained mixture in an organic solvent, adding DDQ at 0 ℃, and stirring at room temperature for 10 hours to obtain the phosphine oxide compound.
Preferably, the inert gas of step S1 includes helium, nitrogen, or argon.
Preferably, the intermediate 1 in step S1 further needs to be post-processed, specifically: cooling, extracting with dichloromethane, removing solvent, and purifying by column chromatography, wherein the eluent used in the column chromatography is petroleum ether.
Preferably, the intermediate 2 in step S2 needs to be further post-processed, specifically: cooling, extracting by dichloromethane, desolventizing, and purifying by column chromatography, wherein an eluent used by the column chromatography is petroleum ether.
Preferably, the intermediate 3 in step S3 further needs to be post-processed, specifically: extracting with ethyl acetate, drying the organic layer with anhydrous sodium sulfate, distilling under reduced pressure, purifying by column chromatography using ethyl acetate and petroleum ether at a ratio of 1: 1(v/v), and drying in vacuum.
Preferably, the phosphine oxide compound in step S4 further needs to be post-treated, specifically: extracting with ethyl acetate, drying the organic layer with anhydrous sodium sulfate, filtering, evaporating, purifying by column chromatography using ethyl acetate and petroleum ether as eluent, wherein the ratio of ethyl acetate to petroleum ether is 1: 1(v/v), and drying in vacuum.
As a preferable possible embodiment, the method for preparing the phosphine oxide compound comprises the steps of:
s1: dissolving 1, 4-dibromo-2-iodobenzene in an organic solvent (tetrahydrofuran or 4-methyltetrahydrofuran), adding isopropyl lithium chloride magnesium chloride at the temperature of-15-20 ℃, stirring for 2-3 h, dropwise adding ethyl formate, extracting with dichloromethane, removing a solvent, and purifying by column chromatography (eluent is petroleum ether) to obtain an intermediate 1;
s2: dissolving the intermediate 1 in an organic solvent (acetic acid or formic acid), dropwise adding hydroiodic acid at normal temperature, heating at 120-130 ℃ for reaction for 2-3 h, cooling, extracting with dichloromethane, removing a solvent, and purifying by column chromatography (an eluent is petroleum ether) to obtain an intermediate 2;
s3: dropwise adding n-butyllithium into the intermediate 2 obtained in the step S2 in an organic solvent (diethyl ether or tetrahydrofuran) at a temperature of-80 to-70 ℃ for reacting for 1-1.5 h, then adding phenylphosphorus dichloride for reacting for 20-30 min, stirring for 12-16 h at a temperature of 20-30 ℃, finally adding hydrogen peroxide and stirring for 2-4 h, extracting with ethyl acetate, drying an organic layer with anhydrous sodium sulfate, carrying out reduced pressure distillation, purifying by column chromatography (eluent is ethyl acetate: petroleum ether is 1: 1(v/v)), and carrying out vacuum drying to obtain the intermediate 2;
s4: performing Suzuki reaction on the intermediate 3 and a donor group, dissolving the obtained mixture in an organic solvent, adding DDQ at the temperature of-5-0 ℃, stirring at room temperature for 10-15 h, extracting with ethyl acetate, drying an organic layer with anhydrous sodium sulfate, filtering, evaporating, purifying by column chromatography, and drying in vacuum, wherein an eluent used in the column chromatography is ethyl acetate and petroleum ether which are 1: 1(v/v), so as to obtain the phosphine oxide compound;
wherein the donor group is 9-phenyl-9H-carbazole or triphenylamine.
The phosphine oxide compound has better luminous intensity, thermal stability and fluorescence quantum yield, provides a new choice for preparing devices with high luminous efficiency, and is suitable for preparing luminescent materials and photoelectric luminescent devices. Therefore, the application of the phosphine oxide compound in the preparation of luminescent materials or photoelectric luminescent devices, and luminescent materials and/or photoelectric luminescent devices comprising the phosphine oxide compound or prepared from the phosphine oxide compound also belong to the protection scope of the invention.
The invention has the following beneficial effects:
1. the compound of the invention takes phosphine oxide as an electron acceptor, and a charge transfer state phosphine oxide compound (A1, A2) with a donor-acceptor structure is constructed by introducing a specific electron donor group into the phosphine oxide compound, has better luminous intensity, thermal stability and fluorescence quantum yield, provides a new choice for preparing devices with high luminous efficiency, and is suitable for preparing luminescent materials and photoelectric luminescent devices.
2. The invention realizes the controllable preparation of the phosphine oxide compound, has low preparation cost and wide raw material sources, and can realize large-scale production.
Drawings
FIG. 1 shows the NMR spectrum of A1 obtained in example 1.
FIG. 2 is a NMR spectrum of product A2 obtained in example 2.
FIG. 3 is a mass spectrum of product A1 obtained in example 1.
FIG. 4 is a mass spectrum of product A2 obtained in example 2.
FIG. 5 is a graph showing an ultraviolet-visible absorption spectrum and a fluorescence emission spectrum of the product A1 obtained in example 1 in a toluene solution.
FIG. 6 is a graph showing an ultraviolet-visible absorption spectrum and a fluorescence emission spectrum of the product A2 obtained in example 2 in a toluene solution.
FIG. 7 is a fluorescence spectrum showing the change in fluorescence intensity before and after bubbling nitrogen gas through the product A1 obtained in example 1.
FIG. 8 is a fluorescence spectrum of a change in fluorescence intensity before and after bubbling nitrogen gas through the product A2 obtained in example 2.
FIG. 9 shows fluorescence emission spectra of films obtained in examples 1-2.
FIG. 10 is a graph showing the fluorescence lifetime of a thin film made of the product obtained in example 1.
FIG. 11 is a graph showing the fluorescence lifetime of a thin film made of the product obtained in example 2.
FIG. 12 is a graph showing the temperature-dependent fluorescence lifetime of a thin film made of the product obtained in example 1.
FIG. 13 is a graph showing the temperature-dependent fluorescence lifetime of a thin film made of the product obtained in example 2.
FIG. 14 is a graph showing normal-temperature fluorescence and low-temperature phosphorescence of the product obtained in example 1 in a toluene solution.
FIG. 15 is a graph showing normal temperature fluorescence and low temperature phosphorescence of the product of example 1 in toluene solution.
FIG. 16 is a thermogravimetric analysis chart of the product obtained in examples 1-2.
Detailed Description
The invention is further described with reference to the drawings and specific examples, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
EXAMPLE 1 preparation of a Phosphino Compound-A Compound of formula (A1)
S1, preparation of an intermediate 1, namely bis (2, 5-dibromophenyl) methanol:
to isopropyl lithium chloride magnesium chloride (2.5M in THF, 4mL, 10mmol) was added dropwise a solution of 1, 4-dibromo-2-iodobenzene (10.4mmol) in THF (5.0mL) at-15 ℃. After stirring for 2 hours, a solution of ethyl formate (5.04mmol, 0.41mL) in THF (2.0mL) was added dropwise. The reaction mixture was stirred at-15 ℃ for a further 0.5h and then warmed to room temperature. The reaction mixture was quenched with saturated ammonium chloride solution (5mL) and water (30 mL). The mixture was extracted with ethyl acetate (3X 30 mL). The combined organic layers were washed with brine, dried over sodium sulfate, filtered and concentrated in vacuo. The crude material was purified by flash chromatography (silica, petroleum ether solution) to yield 1.67g of intermediate 1 (yield: 65.63%). The reaction equation is as follows:
s2, preparing an intermediate 2-3 bis (2, 5-dibromophenyl) methane:
to a solution of intermediate 1(3.28mmol) in acetic acid (10.5mL) was slowly added hydroiodic acid (55% solution) (7.96 mmol). After addition, the mixture was warmed to 130 ℃ and reacted in an oil bath for 2 h. The reaction mixture was cooled to room temperature and stirred for 14 h. The reaction mixture was quenched with saturated sodium sulfite solution (10mL) and water (20 mL). The mixture was extracted with ethyl acetate (3X 20 mL). The combined organic layers were washed with 50% sodium hydroxide solution until the pH of the aqueous phase was > 8, then brine, dried over sodium sulfate, filtered and concentrated in vacuo. The crude material was purified by flash chromatography (silica, petroleum ether) to yield 1.02g of intermediate 2 (yield: 64%). The reaction equation is as follows:
s3, preparing an intermediate 3-2, 8-dibromo-5-phenyl-10H-acridine phosphine 5-oxide:
intermediate 1(0.97g, 2.00mmol) obtained in step S1 was reacted with 47mL of anhydrous tetrahydrofuran at-78 ℃ by dropwise addition of n-butyllithium for 1 hour, followed by further addition of phenylphosphorus dichloride for 20 minutes, followed by stirring at 25 ℃ for 12 hours, followed by dropwise addition of hydrogen peroxide for 2 hours, extraction with ethyl acetate, washing of the combined organic layers with water, drying over anhydrous sodium sulfate, purification of the product after distillation under reduced pressure by silica gel column chromatography (eluent ethyl acetate: petroleum ether ═ 1: 1(v/v)), and drying under vacuum to obtain 0.20g of intermediate 3 as a white solid (yield 22.20%). The reaction equation is as follows:
s4, preparing the compound shown in the formula (I):
the intermediate 3(100mg, 0.223mmol) obtained in step S3, (4- (9H-carbazol-9-yl) phenyl) boronic acid (194mg, 0.67mmol), tetrakis (triphenylphosphine) palladium (15.47mg, 0.013mmol), and potassium carbonate (123.28mg, 0.892mmol) were sequentially added to a 25mL round bottom flask with a reflux condenser, the flask was evacuated and replaced three times with dry nitrogen, then 5mL tetrahydrofuran and 1.5mL deionized water were poured into the flask, refluxed for 12H under nitrogen at 80 ℃, cooled, filtered, extracted with dichloromethane, the organic layer was separated and dried over anhydrous magnesium sulfate, filtered and evaporated to give the crude product. The resulting crude product was dissolved in methanol (10mL, followed by addition of DDQ (323mg, 1.42mmol) at 0 ℃, stirred at room temperature for 10h, then aqueous saturated sodium sulfite, ethyl acetate, aqueous saturated ammonium chloride were added in this order, after filtration, the organic layer was separated, washed with brine 3 times, dried over sodium sulfate, filtered, and concentrated under reduced pressure, the mixture was subjected to silica gel column chromatography (ethyl acetate: petroleum ether ═ 1: 1) to give 125.18mg of compound a1 (yield: 71.34%). the reaction equation is as follows:
EXAMPLE 2 preparation of a phosphine oxide Compound-A Compound of formula (A2)
First, experiment method
The experimental procedure of example 1 was followed, except that (4- (9H-carbazol-9-yl) phenyl) boronic acid was replaced with (4- (diphenylamino) phenyl) boronic acid in step S4.
Example 3 structural characterization and Performance testing
Respectively carrying out nuclear magnetic resonance scanning on the products obtained in the examples 1-2 by adopting a Brooks 400MHz superconducting nuclear magnetic resonance instrument to obtain the products shown in the figures 1-21HMNR graph.
As can be seen from the figure 1 of the drawings,1H NMR(400MHz，CDCl3) δ 8.75-8.73(m, 2H), 8.23(dd, J12.4, 8.1, 3H), 8.14(s, 6H), 8.05-8.01(m, 3H), 7.84-7.78(m, 3H), 7.62-7.58(m, 1H), 7.58-7.56(m, 1H), 7.54(dd, J7.5, 3.1, 3H), 7.52(s, 1H), 7.49(s, 11H), 7.47-7.44(m, 1H), molecular hydrogen spectrum peaks can correspond one-to-one with the target product a1 of example 1, in reasonable amounts;
as can be seen from FIG. 2, 1H NMR (400MHz, CDCl)3) δ 8.59(d, J ═ 2.8, 2H), 7.97(dd, J ═ 12.4, 7.9, 2H), 7.85(d, J ═ 7.9, 2H), 7.58(dd, J ═ 12.8, 7.0, 2H), 7.54 to 7.46(m, 4H), 7.34(ddd, J ═ 11.2, 8.3, 3.9, 3H), 7.23 to 7.17(m, 8H), 7.12 to 7.04(m, 12H), 7.03 to 6.97(m, 4H), molecular hydrogen spectrum peaks can correspond one-to-one with the target product a2 of example 2, and the amounts are reasonable.
(2) Mass spectrum:
5mg of the phosphino-type compound was dissolved in dichloromethane and acetonitrile was added dropwise to 5mL and filtered through a 0.22 μm filter to remove particles above 0.22 μm and minimize detection interference. Then putting the products obtained in the embodiments 1-2 into a liquid phase mass spectrometer, ionizing all components in a sample to generate ions with different charge-mass ratios, forming ion beams under the action of an accelerating electric field, entering a mass analyzer, and causing opposite velocity dispersion by using an electric field and a magnetic field, wherein ions with slower velocity in the ion beams are deflected greatly after passing through the electric field, and the deflection with high velocity is small; ions are deflected in a magnetic field with opposite angular velocity vectors, namely the ions with low speed are still deflected greatly, and the ions with high speed are deflected slightly; when the deflection effects of the two fields compensate each other, their tracks intersect at a point. Meanwhile, mass separation can also occur in the magnetic field, so that ions with the same mass-to-charge ratio and different speeds are focused on the same point, ions with different mass-to-charge ratios are focused on different points, and mass spectrograms of figures 3-4 are obtained by respectively focusing the ions, so that the mass of the ions is determined.
As can be seen from fig. 3, the relative molecular mass of the product obtained in example 1 was 787.26, which is consistent with the relative molecular mass of the phosphine oxide compound (a1) synthesized;
as is clear from fig. 4, the relative molecular mass of the product obtained in example 2 was 791.29, which is consistent with the relative molecular mass of the phosphine oxide compound (a2) synthesized.
Therefore, based on the results of nuclear magnetic resonance and mass spectrometry, the structural formulas of the compounds prepared in examples 1-2 can be determined as shown in the following formulas (I) and (II), respectively:
(3) ultraviolet-visible absorption spectrum and fluorescence spectrum:
ultraviolet visible absorption spectrum: the products obtained in examples 1-2 were dissolved in toluene solution to prepare 1X 10- 3The mol/L mother liquor is respectively diluted to 1 × 10 when being tested by an Shimadzu ultraviolet visible spectrophotometer UV-2700- 5And the ultraviolet-visible absorption spectrums of A1 and A2 in the toluene solution are obtained through testing. Setting parameters; the scanning range is set to be 250-700 nm.
Fluorescence spectrum: the products obtained in examples 1-2 were tested by Edinburgh FL980 transient steady state fluorescence phosphorescence spectrometer to obtain fluorescence emission spectrograms of A1 and A2. Setting parameters: setting excitation wavelength to be 345nm, setting slit width to enable the longitudinal coordinate value to be close to one million, and carrying out spectrum test to obtain a spectrogram.
FIG. 5 is a chart showing an ultraviolet-visible absorption spectrum and a fluorescence emission spectrum of the product A1 obtained in example 1 in a toluene solution, and FIG. 6 is a chart showing an ultraviolet-visible absorption spectrum and a fluorescence emission spectrum of the product A2 obtained in example 2 in a toluene solution. As can be seen from FIGS. 5-6, the main absorption peak positions of A1 and A2 are respectively located at about 327nm and 353nm, the fluorescence emission peak position of A1 is 487nm, the blue light is emitted, the fluorescence emission peak position of A2 is 536nm, and the yellow-green light is emitted.
(4) Change in solution fluorescence intensity
FIGS. 7 to 8 are fluorescence spectra showing changes in fluorescence intensity of the products (A1, A2) obtained in examples 1 to 2 after bubbling nitrogen gas and oxygen gas into a toluene solution at 25 ℃. From fig. 7 to 8, a1 and a2 show higher fluorescence emission intensity in a nitrogen atmosphere than in an oxygen atmosphere, which indicates that oxygen quenches the triplet fluorescence of the phosphine oxide compounds (a1 and a2) to reduce the fluorescence emission intensity, and indicates that the phosphine oxide compounds (a1 and a2) can utilize excitons from the triplet state to achieve higher fluorescence quantum yield.
(5) Fluorescence spectrum of the film:
phosphine oxide compounds (A1 and A2) are doped in commercial host material CBP by a spin coating method according to the dosage of 10 wt% respectively to prepare thin films, and then an Edinburgh FL980 transient stable state fluorescence phosphorescence spectrometer is used for testing respectively to obtain the fluorescence emission spectrum of FIG. 9.
As can be seen from FIG. 9, the phosphor-oxygen compound (A1) has a yellow-green light emission peak position of 527nm after being prepared into a thin film; after the phosphine oxide compound (A2) is prepared into a film, the fluorescence emission peak position is 550nm, and the film belongs to orange yellow light.
(6) Thin film fluorescence lifetime test
The products obtained in examples 1-2 were tested separately using Edinburgh FL980 transient steady state fluorescence phosphorescence spectrophotometers. In the experiment, an excimer laser is used for generating ultraviolet light to excite a sample, the excited fluorescence of the sample enters a photomultiplier through a telescope system, a signal led out by the photomultiplier enters a signal integrator and then enters a computer for data acquisition and processing, and the determination conditions are as follows: the excitation pulse repetition frequency was 1000Hz, the pulse width was 10ns, and the center wavelength was 375 nm.
FIGS. 10 to 11 are graphs showing the fluorescence lifetimes of the doped films of the products (A1, A2) obtained in examples 1 to 2. As can be seen from FIGS. 10 to 11, A1 and A2 have both instant fluorescence lifetime and delayed fluorescence lifetime.
Furthermore, as can be seen from the temperature-dependent fluorescence lifetime graphs of the films prepared in fig. 12 to 13, the lifetime-delayed components of a1 and a2 gradually increase with the increase of temperature, and a1 and a2 have the property of thermally activating the delayed fluorescence. The phosphine oxide compounds (A1 and A2) are shown to be capable of utilizing excitons from triplet states, break through 25% of exciton utilization of the traditional fluorescent materials, and achieve higher fluorescence quantum yield.
(7) Testing of singlet and triplet energy level differences
FIGS. 14 to 15 are graphs of normal-temperature fluorescence and low-temperature phosphorescence of the product obtained in example 1 in a toluene solution. From fig. 14, it can be seen that the singlet and triplet energy levels of a1 were 2.94eV and 2.68eV, respectively, and further that the difference between the singlet and triplet energy levels was 0.26 eV. From fig. 15, it can be seen that the singlet and triplet energy levels of a2 were 2.63eV and 2.59eV, respectively, and the difference between the singlet and triplet energy levels was 0.04 eV. It is demonstrated that a2 has smaller difference in singlet and triplet energy levels, which more easily realizes the property of thermally activated delayed fluorescence.
(8) Fluorescence quantum yield test:
the instrument comprises the following steps: edinburgh FL980 transient steady state fluorescence phosphorescence spectrometer; the test method comprises the following steps: the parameters are set, the optimal excitation wavelength of the product is 375nm for excitation, quinine sulfate is used as a reference, the excitation and the emission slit width are kept consistent, and the results show that the fluorescence quantum yield of the phosphine-oxygen compounds (A1 and A2) of the examples 1 and 2 is 85.78% and 95.14% respectively, which indicates that the phosphine-oxygen compounds have better fluorescence quantum yield.
(9) Thermogravimetric analysis:
thermogravimetric analysis was performed on the phosphine-oxygen compounds (a1 and a2) with a high-temperature synchronous thermal analyzer, respectively, to obtain the thermogravimetric analysis chart of fig. 16. The measurement conditions were as follows: under the protection of nitrogen, the heating rate is 10 ℃/min, and the measurement temperature range is 30-800 ℃.
As can be seen from FIG. 16, the phosphine oxide compounds (A1 and A2) exhibited thermal decomposition temperatures (T) as high as 432 ℃ and 430 ℃ respectivelyd) The method has the advantages of high stability at high temperature, high thermal stability and capability of providing necessary conditions for manufacturing devices by a vacuum evaporation process.
In conclusion, the phosphine oxide compound prepared by the invention has better luminous intensity, thermal stability and fluorescence quantum yield, provides a new choice for preparing a device with high luminous efficiency, and is suitable for preparing a luminescent material and a photoelectric luminescent device.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A phosphine oxide compound with a heat-activated delayed fluorescence property, wherein the phosphine oxide compound has a structural formula as follows:
r is
Or alternatively
2. The phosphine oxide compound with the heat-activated delayed fluorescence property according to claim 1, wherein the phosphine oxide compound has a structural formula shown as A1:
3. the phosphine oxide compound with the heat-activated delayed fluorescence property according to claim 1, wherein the phosphine oxide compound has a structural formula shown as A2:
4. the method for producing a phosphine oxide compound having a thermally activated delayed fluorescence according to claim 1, comprising the steps of:
s1: dissolving 1, 4-dibromo-2-iodobenzene in an organic solvent, adding isopropyl lithium chloride and magnesium chloride into inert gas at the temperature of between 15 ℃ below zero and 20 ℃ below zero, stirring for 2 to 3 hours, and then dropwise adding ethyl formate to obtain an intermediate 1;
the mol ratio of the 1, 4-dibromo-2-iodobenzene to the isopropyl lithium chloride magnesium chloride to the ethyl formate is as follows: 1: 1-1.2: 0.5-0.7;
s2: dissolving the intermediate 1 in an organic solvent, dropwise adding hydroiodic acid at normal temperature, and heating to react to obtain an intermediate 2;
the molar ratio of the intermediate 1 to the hydroiodic acid is as follows: 1: 2-2.5;
s3: sequentially adding n-butyl lithium and phenyl phosphorus dichloride into the intermediate 1 obtained in the step S2 at an organic solvent temperature of-80 to-70 ℃ for reaction, stirring for 12-16 h, and then adding hydrogen peroxide for reaction to obtain an intermediate 3;
the molar ratio of the intermediate 2 to the n-butyllithium to the phenylphosphonium dichloride to the hydrogen peroxide is 1: 2.0-2.3: 1-2: 3-4;
s4: performing Suzuki reaction on the intermediate 3 and a donor group, dissolving the obtained mixture in an organic solvent, adding DDQ at the temperature of-5-0 ℃, and stirring at room temperature for 10-15 hours to obtain the phosphine oxide compound;
the molar ratio of the obtained mixture to DDQ is as follows: 1: 2-2.5.
5. The method for preparing a phosphino-oxygen-type compound with a thermally-activated delayed fluorescence property as claimed in claim 4, wherein said donor group is 9-phenyl-9H-carbazole or triphenylamine.
6. The method for preparing the phosphine oxide compound with the thermally activated delayed fluorescence property according to claim 4, wherein the organic solvent in step S1 is tetrahydrofuran or 4-methyltetrahydrofuran; step S2, the organic solvent is acetic acid or formic acid; step S3, the organic solvent is tetrahydrofuran, diethyl ether or toluene; the organic solvent in step S4 is methanol or ethanol.
7. Use of the phosphine-oxygen compound with thermally activated delayed fluorescence property according to claim 1 in the preparation of luminescent materials or optoelectronic luminescent devices.
8. A luminescent material comprising the phosphine oxide compound having a thermally-activated delayed fluorescence property according to claim 1 or produced from the phosphine oxide compound having a thermally-activated delayed fluorescence property according to claim 1.
9. A luminescent device comprising the phosphine oxide compound having a thermally-activated delayed fluorescence property according to claim 1 or produced from the phosphine oxide compound having a thermally-activated delayed fluorescence property according to claim 1.
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