CN114716479B - 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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- CN114716479B CN114716479B CN202210490183.4A CN202210490183A CN114716479B CN 114716479 B CN114716479 B CN 114716479B CN 202210490183 A CN202210490183 A CN 202210490183A CN 114716479 B CN114716479 B CN 114716479B
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- phosphine oxide
- oxide compound
- organic solvent
- delayed fluorescence
- temperature
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- -1 Phosphine oxide compound Chemical class 0.000 title claims abstract description 70
- 230000003111 delayed effect Effects 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000007725 thermal activation Methods 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 36
- 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 28
- 239000000463 material Substances 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 22
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- VLRYPRKTXDPVNN-UHFFFAOYSA-N 1,4-dibromo-2-iodobenzene Chemical compound BrC1=CC=C(Br)C(I)=C1 VLRYPRKTXDPVNN-UHFFFAOYSA-N 0.000 claims description 11
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 11
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- IMDXZWRLUZPMDH-UHFFFAOYSA-N dichlorophenylphosphine Chemical compound ClP(Cl)C1=CC=CC=C1 IMDXZWRLUZPMDH-UHFFFAOYSA-N 0.000 claims description 10
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 9
- 229940071870 hydroiodic acid Drugs 0.000 claims description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 6
- 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 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
- VIJYEGDOKCKUOL-UHFFFAOYSA-N 9-phenylcarbazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2C2=CC=CC=C21 VIJYEGDOKCKUOL-UHFFFAOYSA-N 0.000 claims description 4
- BBXYLNWQWQDMIL-UHFFFAOYSA-N [Li]C(C)C.Cl Chemical compound [Li]C(C)C.Cl BBXYLNWQWQDMIL-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 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 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
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 238000001994 activation Methods 0.000 claims 2
- 230000004913 activation Effects 0.000 claims 2
- 230000005693 optoelectronics Effects 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 6
- 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 2
- 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 abstract 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 36
- 239000000047 product Substances 0.000 description 31
- 239000000243 solution Substances 0.000 description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 238000004440 column chromatography Methods 0.000 description 13
- 238000002189 fluorescence spectrum Methods 0.000 description 13
- 239000003208 petroleum Substances 0.000 description 12
- 239000010408 film Substances 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 9
- 239000012044 organic layer Substances 0.000 description 9
- 238000006862 quantum yield reaction Methods 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
- 238000000862 absorption spectrum Methods 0.000 description 7
- 239000003480 eluent Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 230000001052 transient effect Effects 0.000 description 4
- 238000001291 vacuum drying Methods 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
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000001419 dependent effect Effects 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000008204 material by function Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical class [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 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
- 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
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 230000008859 change Effects 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
- 238000010586 diagram Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000003810 ethyl acetate extraction Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000003818 flash chromatography Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 238000001819 mass spectrum 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
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- QEKPWRNDDHNEJE-UHFFFAOYSA-N (2,5-dibromophenyl)methanol Chemical compound OCC1=CC(Br)=CC=C1Br QEKPWRNDDHNEJE-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- JOMZGHNBWARSSN-UHFFFAOYSA-N ClP(Cl)(Cl)C1=CC=CC=C1 Chemical compound ClP(Cl)(Cl)C1=CC=CC=C1 JOMZGHNBWARSSN-UHFFFAOYSA-N 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
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 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
- 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
- 229910001873 dinitrogen 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
- 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000012736 patent blue V Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000012545 processing Methods 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
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000005292 vacuum distillation 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
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- 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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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- 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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- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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- 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
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Abstract
The invention provides a phosphine oxide compound with thermal activation delayed fluorescence property, and preparation and application thereof, wherein the phosphine oxide compound has the structural formula:r isOr alternativelyThe compound takes phosphine oxide and carbonyl as acceptors, and a specific electron donor group is introduced into the phosphine oxide to construct a charge transfer compound with a donor-acceptor structure, so that the superposition of front line molecular orbits is reduced, the energy level difference of a singlet state and a triplet state is reduced, a traversing process between opposite systems is activated to realize delayed fluorescence emission, and the utilization rate of excitons of the device is improved.
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
The organic light-emitting diode (OLED) has the advantages of self-luminescence, quick response, wide visibility, low driving voltage, energy saving, light weight, flexible processing and the like, and greatly meets the requirement of consumers on continuous updating of display technology. Meanwhile, the OLED also has wide application prospect and huge market demand in the field of illumination.
Organic electroluminescent devices (organic EL devices) can be classified into fluorescent type and phosphorescent type according to the principle of luminescenceBoth types. To the organic EL element, a voltage is applied, 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 statistics, singlet excitons and triplet excitons are generated in a ratio of 25% to 75%. Since fluorescence type uses singlet excitons to emit light, the internal quantum efficiency can only reach 25%. Thermally Active Delayed Fluorescence (TADF) materials are third generation organic luminescent materials that develop subsequent to organic fluorescent materials and organic phosphorescent materials. Such materials generally have a small singlet-triplet energy level difference (E st ) The triplet state excitons can be converted into singlet state excitons through inverse gap crossing to emit light, the singlet state excitons and the triplet state excitons formed under electric excitation can be fully utilized, the internal quantum efficiency of the device can reach 100%, meanwhile, the material structure is controllable, the property is stable, the price is low, noble metals are not needed, and the application prospect in the field of OLEDs is wide.
In order to prepare a high-performance OLED light emitting device, a high-performance OLED functional material needs to be selected and used, and the following basic requirements are required for the OLED functional materials with different roles:
1. the material has good thermal stability, namely the material is not 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, is required to have better efficiency, longer service life and lower voltage. This requires materials with the appropriate highest molecular occupied orbitals, lowest molecular unoccupied orbitals (HOMO, LUMO), and appropriate triplet energies.
In recent years, although some breakthrough has been made in the development of OLED functional materials, as lighting or display applications, there is a need to discover and innovate materials with better properties, in particular, organic functional materials with better properties with high efficiency, which can be applied to TADF systems.
Disclosure of Invention
In view of the above, the present invention aims to provide 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-mentioned phosphine oxide compound.
A third object of the present invention is to provide an application of the above-mentioned phosphine oxide compound in preparing a luminescent material or a photoelectric luminescent device.
A fourth object of the present invention is to provide a luminescent material.
A fifth object of the present invention is to provide a photo-luminescent device.
To achieve the above object, a first technical solution of the present invention is as follows:
the invention provides a phosphine oxide compound with a thermal activation delayed fluorescence property, which has the following structural formula:
r isOr->
Specifically, the phosphine oxide compound has a chemical structure shown in the following formula (I) or formula (II):
the second technical purpose of the invention is to provide a preparation method of the phosphine oxide compound, which comprises the following steps:
s1: dissolving 1, 4-dibromo-2-iodobenzene in an organic solvent, adding isopropyl lithium chloride magnesium chloride under inert gas at the temperature of-15 ℃, stirring for 2 hours, and then dropwise adding ethyl formate to obtain an intermediate 1;
s2: dissolving the intermediate 1 in an organic solvent, dripping hydroiodic acid at normal temperature, and performing heating reaction to obtain an intermediate 2;
s3: sequentially adding n-butyllithium 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: performing 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 magnesium chloride and the ethyl formate in the step S1 is as follows: 1:1-1.2:0.5-0.7.
Most preferably, the molar ratio of the 1, 4-dibromo-2-iodobenzene, the isopropyl lithium magnesium chloride and the ethyl formate is as follows: 1:1:0.5.
Preferably, in step S2, the molar ratio of the intermediate 1 to the hydroiodic acid is: 1:2-2.5.
Most preferably, the molar ratio of the intermediate 1 to the hydroiodic acid in the step S2 is: 1:2.4.
Preferably, the molar ratio of the intermediate 1, the n-butyllithium, the phenyl phosphorus dichloride and the hydrogen peroxide in the step S3 is 1:2.0-2.3:1-2:3-4.
Most preferably, the molar ratio of the intermediate 1, n-butyllithium, phenyl phosphorus dichloride and hydrogen peroxide in the step S3 is as follows: 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, DDQ, is: 1:2.4.
Preferably, the organic solvent in step S1 is tetrahydrofuran or 4-methyltetrahydrofuran. Most preferred is tetrahydrofuran.
Preferably, the organic solvent in step S2 is acetic acid or formic acid. Most preferably acetic acid.
Preferably, the organic solvent in step S3 is tetrahydrofuran, diethyl ether or toluene. Most preferred is tetrahydrofuran.
Preferably, the organic solvent in step S4 is methanol or ethanol. Most preferred is methanol.
Preferably, step S1 is specifically: 1, 4-dibromo-2-iodobenzene is dissolved in an organic solvent, isopropyl lithium chloride magnesium chloride is added at the temperature of-15 to 20 ℃, and ethyl formate is added dropwise after stirring for 2 to 3 hours, so as to obtain an intermediate 1.
Most preferably, step S1 is specifically: 1, 4-dibromo-2-iodobenzene is dissolved in an organic solvent, isopropyl lithium chloride and magnesium chloride are added at the temperature of minus 15 ℃, and ethyl formate is added dropwise after stirring for 2 hours, so as to obtain an intermediate 1.
Preferably, the heating temperature in the step S2 is 120-130 ℃ and the heating time is 2-3 h.
Preferably, the heating temperature in step S2 is 130 ℃ and the time is 3h.
Preferably, step S3 is specifically: dropwise adding n-butyllithium into the intermediate 1 obtained in the step S2 at the temperature of-80 to-70 ℃ for reaction for 1-1.5 h, adding phenyl phosphorus dichloride for reaction for 20-30 min, stirring for 12-16 h at the temperature of 20-30 ℃, and finally adding hydrogen peroxide for stirring for 2-4 h to obtain the intermediate 2.
Most preferably, step S3 is specifically: and (2) dropwise adding n-butyllithium into the intermediate 1 obtained in the step (S2) at the temperature of diethyl ether or tetrahydrofuran and minus 78 ℃ for reaction for 1h, adding phenyl phosphorus dichloride for reaction for 20min, stirring for 12h at the temperature of 25 ℃, and finally adding hydrogen peroxide and stirring for 2h to obtain the intermediate 2.
Preferably, step S4 is specifically: and (3) 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 h to obtain the phosphine oxide compound.
Most preferably, step S4 is specifically: and (3) performing 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 in step S1 includes helium, nitrogen or argon.
Preferably, the intermediate 1 in step S1 is further subjected to a post-treatment, specifically: cooling, extracting with dichloromethane, desolventizing, and purifying by column chromatography, wherein the eluent used by the column chromatography is petroleum ether.
Preferably, the intermediate 2 in step S2 is further subjected to a post-treatment, specifically: cooling, extracting with dichloromethane, desolventizing, and purifying by column chromatography, wherein the eluent used by the column chromatography is petroleum ether.
Preferably, the intermediate 3 in step S3 is further subjected to a post-treatment, specifically: ethyl acetate extraction, anhydrous sodium sulfate drying of the organic layer, reduced pressure distillation, column chromatography purification, and vacuum drying, wherein the eluent used in the column chromatography is ethyl acetate to petroleum ether=1:1 (v/v).
Preferably, the phosphine oxide compound in step S4 needs to be post-treated, specifically: ethyl acetate extraction, anhydrous sodium sulfate drying of the organic layer, filtration and evaporation, column chromatography purification, and vacuum drying, wherein the eluent used in the column chromatography is ethyl acetate to petroleum ether=1:1 (v/v).
As a preferred embodiment, the process 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 and magnesium chloride at the temperature of-15-20 ℃, stirring for 2-3 hours, then dropwise adding ethyl formate, extracting with dichloromethane, desolventizing, and purifying by column chromatography (eluting with petroleum ether) to obtain an intermediate 1;
s2: dissolving the intermediate 1 in an organic solvent (acetic acid or formic acid), dripping hydroiodic acid at normal temperature, heating at 120-130 ℃ for reaction for 2-3 hours, cooling, extracting with dichloromethane, desolventizing, and purifying by column chromatography (eluting with petroleum ether) to obtain an intermediate 2;
s3: dropwise adding n-butyllithium into the intermediate 2 obtained in the step S2 at the temperature of-80 to-70 ℃ in an organic solvent (diethyl ether or tetrahydrofuran) to react for 1-1.5 h, adding phenyl phosphorus dichloride to react for 20-30 min, stirring for 12-16 h at the temperature of 20-30 ℃, finally adding hydrogen peroxide to stir for 2-4 h, extracting with ethyl acetate, drying an organic layer with anhydrous sodium sulfate, performing reduced pressure distillation, purifying by column chromatography (eluent is ethyl acetate: petroleum ether=1:1 (v/v)), and performing 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-5-0 ℃, stirring at room temperature for 10-15 h, extracting with ethyl acetate, drying an organic layer with anhydrous sodium sulfate, filtering and evaporating, purifying by column chromatography, and vacuum drying, wherein an eluent used by the column chromatography is ethyl acetate to petroleum ether=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 preparing a luminescent material or a photoelectric luminescent device, and the luminescent material and/or the photoelectric luminescent device containing the phosphine oxide compound or prepared from the phosphine oxide compound are also within 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 is a charge transfer state phosphine oxide compound (A1, A2) with a donor-acceptor structure by introducing a specific electron donor group into the phosphine oxide, and 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.
2. The invention realizes 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 is a nuclear magnetic resonance hydrogen spectrum of a product A1 obtained in example 1.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the product A2 obtained in example 2.
FIG. 3 is a mass spectrum of the product A1 obtained in example 1.
FIG. 4 is a mass spectrum of the product A2 obtained in example 2.
FIG. 5 is an ultraviolet-visible absorption spectrum and a fluorescence emission spectrum of the product A1 obtained in example 1 in toluene solution.
FIG. 6 is an ultraviolet-visible absorption spectrum and a fluorescence emission spectrum of the product A2 obtained in example 2 in toluene solution.
FIG. 7 is a graph showing the fluorescence spectrum of the change in fluorescence intensity before and after bubbling nitrogen into the product A1 obtained in example 1.
FIG. 8 is a graph showing the fluorescence spectrum of the change in fluorescence intensity before and after bubbling nitrogen gas into the product A2 obtained in example 2.
FIG. 9 is a graph showing fluorescence emission spectra of films prepared from the products obtained in examples 1 to 2.
FIG. 10 is a graph showing fluorescence lifetime of a thin film formed from the product obtained in example 1.
FIG. 11 is a graph showing fluorescence lifetime of a thin film formed from the product obtained in example 2.
FIG. 12 is a graph of the temperature dependent fluorescence lifetime of the product obtained in example 1 as a film.
FIG. 13 is a graph of the temperature dependent fluorescence lifetime of the product obtained in example 2 as a film.
FIG. 14 is a graph showing fluorescence at normal temperature and phosphorescence at low temperature of the product obtained in example 1 in toluene solution.
FIG. 15 is a graph showing fluorescence at normal temperature and phosphorescence at low temperature of the product obtained in example 1 in toluene solution.
FIG. 16 is a thermogravimetric analysis of the products obtained in examples 1-2.
Detailed Description
The invention is further illustrated in the following drawings and specific examples, which are not intended to limit the invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Reagents and materials used in the following examples are commercially available unless otherwise specified.
Example 1 preparation of a Phosphonoxy Compound-Compound of formula (A1)
S1, preparing an intermediate 1-bis (2, 5-dibromophenyl) methanol:
to magnesium lithium isopropylchloride (2.5M in THF, 4mL,10 mmol) was added dropwise a solution of 1, 4-dibromo-2-iodobenzene (10.4 mmol) in THF (5.0 mL) at-15 ℃. After stirring for 2 hours, a solution of ethyl formate (5.04 mmol,0.41 mL) in THF (2.0 mL) was added dropwise. The reaction mixture was stirred at-15 ℃ for an additional 0.5h and then warmed to room temperature. The reaction mixture was quenched with saturated ammonium chloride solution (5 mL) 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 give 1.67g of intermediate 1 (yield: 65.63%). The reaction equation is shown below:
s2, preparing an intermediate 2-3 bis (2, 5-dibromophenyl) methane:
to a solution of intermediate 1 (3.28 mmol) in acetic acid (10.5 mL) was slowly added hydroiodic acid (55% solution) (7.96 mmol). After the addition, the mixture was warmed to 130 ℃ and reacted in an oil bath for 2h. The reaction mixture was cooled to room temperature and stirred for 14h. The reaction mixture was quenched with saturated sodium sulfite solution (10 mL) 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 with brine, dried over sodium sulfate, filtered and concentrated in vacuo. The crude material was purified by flash chromatography (silica, petroleum ether) to give 1.02g of intermediate 2 (yield: 64%). The reaction equation is shown below:
s3, preparing an intermediate 3-2, 8-dibromo-5-phenyl-10H-acridine phosphine 5-oxide:
intermediate 1 (0.97 g,2.00 mmol) obtained in step S1 was reacted with dropwise addition of n-butyllithium at-78 ℃ in 47mL of anhydrous tetrahydrofuran for 1h, followed by addition of phenylphosphorous chloride for 20min, stirring at 25 ℃ for 12h, then dropwise addition of hydrogen peroxide for 2h, extraction with ethyl acetate, washing the combined organic layers with water, drying with anhydrous sodium sulfate, and vacuum distillation to obtain 0.20g of white solid intermediate 3 (yield 22.20%) after purification by silica gel column chromatography (eluent ethyl acetate: petroleum ether=1:1 (v/v)). The reaction equation is shown below:
s4, preparation of a compound of formula (I):
intermediate 3 (100 mg,0.223 mmol), (4- (9H-carbazol-9-yl) phenyl) boronic acid (194 mg,0.67 mmol), tetrakis (triphenylphosphine) palladium (15.47 mg,0.013 mmol), potassium carbonate (123.28 mg,0.892 mmol) obtained in step S3 were added sequentially to a 25mL round bottom flask with reflux condenser, after the flask was evacuated and replaced three times with dry nitrogen, 5mL tetrahydrofuran and 1.5mL deionized water were injected into the flask, refluxed for 12H at 80℃with nitrogen, cooled, filtered, the organic layer was separated and dried over anhydrous magnesium sulfate, filtered and evaporated to give the crude product. The obtained crude product was dissolved in methanol (10 mL), then DDQ (323 mg,1.42 mmol) was added at 0 ℃ after stirring at room temperature for 10 hours, a saturated aqueous sodium sulfite solution, ethyl acetate, a saturated aqueous ammonium chloride solution were added in this order, after filtration, the organic layer was separated, washed 3 times with brine, 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 obtain 125.18mg of compound A1 (yield: 71.34%). The reaction equation was as follows:
example 2 preparation of a Phosphonoxy Compound-Compound of formula (A2)
1. Experimental method
The experimental procedure of example 1 is repeated, except that (4- (9H-carbazol-9-yl) phenyl) boronic acid is replaced with (4- (diphenylamino) phenyl) boronic acid in step S4.
Example 3 structural characterization and Performance testing
The products obtained in examples 1 and 2 were scanned by nuclear magnetic resonance using a Brookfield 400MHz superconducting NMR spectrometer, respectively, to obtain the products shown in FIGS. 1 and 2 1 HMNR plot.
As can be seen from the figure 1 of the drawings, 1 H NMR(400MHz，CDCl 3 ) Delta=8.75-8.73 (m, 2H), 8.23 (dd, j= 12.4,8.1,3H), 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, j= 7.5,3.1,3H), 7.52 (s, 1H), 7.49 (s, 11H), 7.47-7.44 (m, 1H). Molecular hydrogen spectrum peaks can be in one-to-one correspondence with the target product A1 of example 1, in reasonable numbers;
as can be seen from FIG. 2, 1H NMR (400 MHz, 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, in reasonable numbers.
(2) Mass spectrometry:
5mg of the phosphine oxide compound was dissolved in methylene chloride, acetonitrile was added dropwise to 5mL, and the mixture was filtered through a 0.22 μm filter to remove particles exceeding 0.22. Mu.m, thereby minimizing detection interference. Then respectively placing the products obtained in the examples 1-2 into a liquid-phase mass spectrometer, generating ions with different charge-to-mass ratios by utilizing ionization of each component in a sample, forming an ion beam by the action of an accelerating electric field, entering a mass analyzer, and enabling ions with opposite velocity dispersion, namely ions with lower velocity in the ion beam, to deflect more and deflect less after passing through the electric field by utilizing the electric field and the magnetic field; in the magnetic field, the ions are deflected in opposite angular velocity vectors, namely, the ions with low speed are still deflected greatly, and the deflection with high speed is small; when the deflection effects of the two fields compensate each other, their trajectories intersect at a point. At the same time, 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 the mass spectrograms of fig. 3-4 are obtained by focusing the ions respectively, 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 synthesized phosphine oxide compound (A1);
as can be seen from fig. 4, the product obtained in example 2 had a relative molecular mass of 791.29, which was consistent with the relative molecular mass of the synthesized phosphine oxide compound (A2).
Thus, based on the results of nuclear magnetic resonance and mass spectrometry, it was confirmed that the structural formulas of the compounds prepared in examples 1 to 2 are represented by 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 to prepare 1X 10 - 3 The mol/L mother solution is diluted to 1 multiplied by 10 when being tested by using an Shimadzu ultraviolet visible spectrophotometer UV-2700 - 5 And (3) testing mol/L to obtain ultraviolet visible absorption spectra of A1 and A2 in toluene solution. Setting parameters; the scanning range is set to be 250-700 nm.
Fluorescence spectrum: the products obtained in examples 1-2 were tested by using an Edinburgh FL980 transient steady-state fluorescence phosphorescence spectrometer to obtain fluorescence emission spectra of A1 and A2, respectively. Parameter setting: setting excitation wavelength 345nm, setting slit width to make its ordinate value approximate to one million, and making spectrum test so as to obtain spectrogram.
FIG. 5 is a graph showing the ultraviolet-visible absorption spectrum and the fluorescence emission spectrum of the product A1 obtained in example 1 in toluene solution, and FIG. 6 is a graph showing the ultraviolet-visible absorption spectrum and the fluorescence emission spectrum of the product A2 obtained in example 2 in toluene solution. As can be seen from FIGS. 5 to 6, the main absorption peak positions of A1 and A2 are respectively located at 327nm and 353nm, the fluorescence emission peak position of A1 is 487nm, the sky blue light is emitted, the fluorescence emission peak position of A2 is 536nm, and the yellow-green light is emitted.
(4) Fluorescence intensity variation of solution
FIGS. 7 to 8 are fluorescence spectra showing changes in fluorescence intensity of the products (A1, A2) obtained in examples 1 to 2 after nitrogen and oxygen were blown into toluene solutions, respectively, at 25 ℃. From fig. 7 to 8, it is apparent that A1 and A2 show higher fluorescence emission intensity under a nitrogen atmosphere than under an oxygen atmosphere, indicating that oxygen quenches fluorescence of the phosphine oxide compound (A1 and A2) in a triplet state, and reduces the fluorescence emission intensity thereof, indicating that the phosphine oxide compound (A1 and A2) can realize higher fluorescence quantum yield by using excitons from the triplet state.
(5) Fluorescence spectrum of the film:
phosphine oxide compounds (A1 and A2) are respectively doped into a commercial main material CBP to prepare films in an amount of 10wt% by adopting a spin coating method, and are respectively tested by using an Edinburgh FL980 transient steady-state fluorescence phosphorescence spectrometer to obtain the fluorescence emission spectrum of FIG. 9.
As can be seen from FIG. 9, after the phosphine oxide compound (A1) was prepared into a thin film, the fluorescence emission peak position was 527nm, which is yellow-green light; 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) Film fluorescence lifetime test
The products obtained in examples 1-2 were each tested using an Edinburgh FL980 transient steady state fluorescence phosphorescence spectrometer. The experiment adopts an excimer laser to generate ultraviolet light to excite a sample, fluorescence emitted by 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 to collect and process data, wherein the measurement conditions are as follows: the excitation pulse repetition frequency was 1000Hz, the pulse width was 10ns, and the center wavelength was 375nm.
FIGS. 10 to 11 are graphs showing fluorescence lifetime of the products (A1, A2) obtained in examples 1 to 2 in the doped thin film. From fig. 10 to 11, A1 and A2 have both the instantaneous fluorescence lifetime and the delayed fluorescence lifetime.
Further, as can be seen from the temperature-dependent fluorescence lifetime graphs of the films formed in FIGS. 12 to 13, the delayed fluorescence lifetime of A1 and A2 gradually increases with increasing temperature, and A1 and A2 have the property of thermally activating delayed fluorescence at the same time. The phosphine oxide compounds (A1 and A2) can utilize excitons from triplet states, break through 25% of exciton utilization of the traditional fluorescent materials, and realize higher fluorescence quantum yield.
(7) Testing of the level differences of the singlet and triplet states
FIGS. 14 to 15 are fluorescent and phosphorescent diagrams at normal temperature in toluene solution of the product obtained in example 1. From FIG. 14, the singlet and triplet energy levels of A1 were 2.94eV and 2.68eV, respectively, and further the singlet and triplet energy level difference was 0.26eV. From FIG. 15, 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 0.04eV. A2 is illustrated to have smaller singlet and triplet energy level differences, which more readily achieve the property of thermally activated delayed fluorescence.
(8) Fluorescence quantum yield test:
instrument: edinburgh FL980 transient steady-state fluorescence phosphorescence spectrometer; the testing method comprises the following steps: the fluorescence quantum yields of the phosphine oxide compounds (A1 and A2) of examples 1 and 2 are 85.78% and 95.14% respectively, which shows that the phosphine oxide compounds of the invention have better fluorescence quantum yields.
(9) Thermogravimetric analysis:
and respectively carrying out thermogravimetric analysis on the phosphine oxide compounds (A1 and A2) by adopting a high-temperature synchronous thermal analyzer to obtain a thermogravimetric analysis diagram of FIG. 16. Measurement conditions: under the protection of nitrogen, the temperature rising 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) exhibit thermal decomposition temperatures (T) of up to 432℃and 430℃respectively d ) The film is relatively stable at a higher temperature, has better thermal stability and provides 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 devices with high luminous efficiency, and is suitable for preparing luminescent materials and photoelectric luminescent devices.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (8)
1. A phosphine oxide compound with thermal activation delayed fluorescence property, which is characterized in that the phosphine oxide compound has the following structural formula:
；
r isOr->；
Which is prepared by the following steps:
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-15 to-20 ℃, stirring for 2-3 hours, and then dropwise adding ethyl formate to obtain an intermediate 1 bis (2, 5-dibromophenyl) methanol;
the molar ratio of the 1, 4-dibromo-2-iodobenzene to the isopropyl lithium magnesium chloride to the ethyl formate is as follows: 1:1 to 1.2:0.5 to 0.7; s2: dissolving the intermediate 1 in an organic solvent, dripping hydroiodic acid at normal temperature, and performing a heating reaction to obtain an intermediate 2 bis (2, 5-dibromophenyl) methane;
the molar ratio of the intermediate 1 to the hydroiodic acid is as follows: 1:2-2.5;
s3: sequentially adding n-butyllithium and phenyl phosphorus dichloride into the intermediate 2 obtained in the step S2 at the temperature of-80 to-70 ℃ in an organic solvent, stirring for 12-16 hours, and adding hydrogen peroxide for reaction to obtain an intermediate 3, 8-dibromo-5-phenyl-10H-acridine phosphine 5-oxide;
the molar ratio of the intermediate 2 to the n-butyllithium to the phenyl phosphorus dichloride to the hydrogen peroxide is 1:2.0 to 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;
the donor group in S4 is 9-phenyl-9H-carbazole or triphenylamine.
2. The phosphine oxide compound with heat activation delayed fluorescence property according to claim 1, wherein the phosphine oxide compound has a structural formula shown in A1:
。
3. the phosphine oxide compound with heat activation delayed fluorescence properties according to claim 1, wherein the phosphine oxide compound has a structural formula shown in A2:
。
4. the method for preparing a phosphine oxide compound having a delayed fluorescence property by thermal activation as claimed in 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-15 to-20 ℃, stirring for 2-3 hours, and then dropwise adding ethyl formate to obtain an intermediate 1 bis (2, 5-dibromophenyl) methanol;
the molar ratio of the 1, 4-dibromo-2-iodobenzene to the isopropyl lithium magnesium chloride to the ethyl formate is as follows: 1:1 to 1.2:0.5 to 0.7; s2: dissolving the intermediate 1 in an organic solvent, dripping hydroiodic acid at normal temperature, and performing a heating reaction to obtain an intermediate 2 bis (2, 5-dibromophenyl) methane;
the molar ratio of the intermediate 1 to the hydroiodic acid is as follows: 1:2-2.5;
s3: sequentially adding n-butyllithium and phenyl phosphorus dichloride into the intermediate 2 obtained in the step S2 at the temperature of-80 to-70 ℃ in an organic solvent, stirring for 12-16 hours, and adding hydrogen peroxide for reaction to obtain an intermediate 3, 8-dibromo-5-phenyl-10H-acridine phosphine 5-oxide;
the molar ratio of the intermediate 2 to the n-butyllithium to the phenyl phosphorus dichloride to the hydrogen peroxide is 1:2.0 to 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;
the donor group in S4 is 9-phenyl-9H-carbazole or triphenylamine.
5. The method for preparing a phosphine oxide compound having a delayed fluorescence property by thermal activation according to claim 4, wherein the organic solvent in step S1 is tetrahydrofuran or 4-methyltetrahydrofuran; the organic solvent in the step S2 is acetic acid or formic acid; the organic solvent in the step S3 is tetrahydrofuran, diethyl ether or toluene; the organic solvent in the step S4 is methanol or ethanol.
6. Use of the phosphine oxide compound with thermal activation delayed fluorescence property as defined in claim 1 in preparation of luminescent material or photoelectric luminescent device.
7. A luminescent material comprising the phosphine oxide compound having a thermally activated delayed fluorescence property according to claim 1 or prepared from the phosphine oxide compound having a thermally activated delayed fluorescence property according to claim 1.
8. An optoelectronic light emitting device comprising the phosphine oxide compound having the thermally activated delayed fluorescence property of claim 1 or prepared from the phosphine oxide compound having the thermally activated delayed fluorescence property of claim 1.
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