CN105924472A - Triphenyl phosphorus oxide-based thermal excitation delayed fluorescent blue light guest material and its preparation method and use - Google Patents
Triphenyl phosphorus oxide-based thermal excitation delayed fluorescent blue light guest material and its preparation method and use Download PDFInfo
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- CN105924472A CN105924472A CN201610272846.XA CN201610272846A CN105924472A CN 105924472 A CN105924472 A CN 105924472A CN 201610272846 A CN201610272846 A CN 201610272846A CN 105924472 A CN105924472 A CN 105924472A
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- blue light
- thermal excitation
- triphenyl phosphorus
- delayed fluorescence
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- 239000000463 material Substances 0.000 title claims abstract description 145
- 230000003111 delayed effect Effects 0.000 title claims abstract description 128
- 230000005284 excitation Effects 0.000 title claims abstract description 127
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 title abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 109
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 44
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims abstract description 29
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 27
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001953 recrystallisation Methods 0.000 claims abstract description 7
- DHNRAGGXWCCERB-UHFFFAOYSA-N [O].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 Chemical compound [O].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 DHNRAGGXWCCERB-UHFFFAOYSA-N 0.000 claims description 115
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 111
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 55
- 238000004440 column chromatography Methods 0.000 claims description 53
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 48
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 47
- 238000000746 purification Methods 0.000 claims description 31
- OIRHKGBNGGSCGS-UHFFFAOYSA-N 1-bromo-2-iodobenzene Chemical compound BrC1=CC=CC=C1I OIRHKGBNGGSCGS-UHFFFAOYSA-N 0.000 claims description 27
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 27
- 239000003208 petroleum Substances 0.000 claims description 24
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 24
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 claims description 15
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 11
- 229950000688 phenothiazine Drugs 0.000 claims description 10
- JSEQNGYLWKBMJI-UHFFFAOYSA-N 9,9-dimethyl-10h-acridine Chemical compound C1=CC=C2C(C)(C)C3=CC=CC=C3NC2=C1 JSEQNGYLWKBMJI-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 9
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 7
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims description 3
- QNEFNFIKZWUAEQ-UHFFFAOYSA-N carbonic acid;potassium Chemical compound [K].OC(O)=O QNEFNFIKZWUAEQ-UHFFFAOYSA-N 0.000 claims 3
- 230000005540 biological transmission Effects 0.000 abstract description 15
- 239000000203 mixture Substances 0.000 abstract description 14
- 238000002347 injection Methods 0.000 abstract description 13
- 239000007924 injection Substances 0.000 abstract description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000004587 chromatography analysis Methods 0.000 abstract 1
- 238000004020 luminiscence type Methods 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 92
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 57
- 238000005401 electroluminescence Methods 0.000 description 21
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- ATTVYRDSOVWELU-UHFFFAOYSA-N 1-diphenylphosphoryl-2-(2-diphenylphosphorylphenoxy)benzene Chemical group C=1C=CC=CC=1P(C=1C(=CC=CC=1)OC=1C(=CC=CC=1)P(=O)(C=1C=CC=CC=1)C=1C=CC=CC=1)(=O)C1=CC=CC=C1 ATTVYRDSOVWELU-UHFFFAOYSA-N 0.000 description 13
- 238000001228 spectrum Methods 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000001704 evaporation Methods 0.000 description 12
- 230000008020 evaporation Effects 0.000 description 12
- 239000000284 extract Substances 0.000 description 12
- 239000012044 organic layer Substances 0.000 description 12
- 238000002411 thermogravimetry Methods 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 230000004888 barrier function Effects 0.000 description 10
- 230000000903 blocking effect Effects 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- 239000004033 plastic Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229910015711 MoOx Inorganic materials 0.000 description 6
- 206010037660 Pyrexia Diseases 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 238000005336 cracking Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000027756 respiratory electron transport chain Effects 0.000 description 6
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 5
- 238000010030 laminating Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000010189 synthetic method Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000005538 encapsulation Methods 0.000 description 4
- 230000005311 nuclear magnetism Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- 238000007738 vacuum evaporation Methods 0.000 description 4
- 230000035939 shock Effects 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- SCHRRICRQNJJKN-UHFFFAOYSA-N P.[O] Chemical group P.[O] SCHRRICRQNJJKN-UHFFFAOYSA-N 0.000 description 2
- XCQQWDCKLLORFE-UHFFFAOYSA-N [O].C1(=CC=CC=C1)PC1=CC=CC=C1 Chemical compound [O].C1(=CC=CC=C1)PC1=CC=CC=C1 XCQQWDCKLLORFE-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- ZABORCXHTNWZRV-UHFFFAOYSA-N 10-[4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl]phenoxazine Chemical compound O1C2=CC=CC=C2N(C2=CC=C(C=C2)C2=NC(=NC(=N2)C2=CC=CC=C2)C2=CC=CC=C2)C2=C1C=CC=C2 ZABORCXHTNWZRV-UHFFFAOYSA-N 0.000 description 1
- GGUFVZFOCZNPEG-UHFFFAOYSA-N 4,5,6-triphenyltriazine Chemical compound C1=CC=CC=C1C1=NN=NC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 GGUFVZFOCZNPEG-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- ZNSDNJGLCKLLQW-UHFFFAOYSA-N [O].C1(=CC=CC=C1)[P] Chemical compound [O].C1(=CC=CC=C1)[P] ZNSDNJGLCKLLQW-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 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
- C07F9/6527—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and oxygen atoms as the only ring hetero atoms
- C07F9/6533—Six-membered rings
- C07F9/65335—Six-membered rings condensed with carbocyclic rings or carbocyclic ring systems
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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
- C07F9/6536—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and sulfur atoms with or without oxygen atoms, as the only ring hetero atoms
- C07F9/6544—Six-membered rings
- C07F9/6547—Six-membered rings condensed with carbocyclic rings or carbocyclic ring systems
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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- 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
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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
- C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
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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
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
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- Electroluminescent Light Sources (AREA)
Abstract
The invention relates to a fluorescent blue light guest material and its preparation method and use and especially relates to a triphenyl phosphorus oxide-based thermal excitation delayed fluorescent blue light guest material and its preparation method and use. The triphenyl phosphorus oxide-based thermal excitation delayed fluorescent blue light guest material solves the problem that because of large difference of an electron donor and an acceptor, when the electron donor is increased, guest emission wavelength produces red shift so that stable and efficient blue guest luminescence cannot be realized. The blue light guest material has a structural formula shown in the description. The preparation method comprises 1, preparing PXZPhBr, PXZPhBr, PTZPhBr and DMACPhBr, 2, mixing the products obtained through the step 1 and tetrahydrofuran, adding n-butyllithium and diphenylphosphinous chloride into the mixture, adding hydrogen peroxide into the mixture, carrying out stirring and carrying out chromatography and recrystallization. The triphenyl phosphorus oxide-based thermal excitation delayed fluorescent blue light guest material is used for preparation of a thermal excitation delayed fluorescent electroluminescent device. The material utilizes short-axis modification strategy, effectively keeps a matrix triplet state energy level, has a donor-acceptor (D-A)-type molecular structure and balances carrier injection and transmission. The preparation method belongs to the field of fluorescent material preparation.
Description
Technical field
The present invention relates to a kind of fluorescence blue light guest materials, preparation method and application.
Background technology
21st century is informationized society.The fast development of Internet technology, makes people become i.e. in information communication
Time, convenient, efficient, it is also proposed higher requirement, such as superior performance simultaneously for equipment, small and exquisite portable etc..This history
The moment of property, owing to organic electroluminescence device (Organic Light Emitting Diode:OLED) and organic electroluminescence are sent out
Luminescent material receives the favor of scientist.OLED has the characteristics such as active illuminating, high brightness, low energy consumption, ultra-thin, wide viewing angle, quilt
Research staff becomes " fantasy display ".Electroluminescent fluorescent and electroluminescent phosphorescence are referred to as the first generation and second filial generation OLED.Currently,
Thermal excitation delayed fluorescence receives widely to be paid close attention to, and is referred to as third generation OLED.
Currently, thermal excitation delayed fluorescence guest materials molecular structure is mainly made up of electron donor and electron acceptor.Electronics
Donor and receptor form electronics push-pull configuration, make molecular distortion, with the transmission of balancing charge.But, due to electron donor be subject to
The strength difference of body is big, and when causing increasing electron donor, object transmitted wave length red shift occurs, thus can not realize stable, efficient
Blue guest luminous.Such as, before this Adachi seminar deliver with 2,4,6-triphenyls-1,3,5-triazines is that electronics is subject to
Body, phenoxazine is electron donor, and PXZ-TRZ, bis-PXZ-TRZ, the tri-PXZ-TRZ of synthesis, due to the suction of triphenyl triazine
Electronic capability is too strong, increases the quantity of phenoxazine, and the transmitted wave length of object occurs in that obvious red shift.
Summary of the invention
The invention aims to solve, owing to the strength difference of electron donor and receptor is big, to cause increasing electron donor
Time, there is red shift, thus can not realize technical problem stable, that efficient blue guest is luminous in object transmitted wave length, it is provided that
A kind of thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen, preparation method and application its prepare electroluminescent cell
The method of part.
The structural formula of thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen is as follows:
Wherein R group is
X is
The preparation method of thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen is as follows:
Bromo-iodobenzene, 0.1～0.5mmol Hydro-Giene (Water Science)., 1～5mmol potassium carbonate are put by 1mmol phenoxazine, 1～5mmol
In round-bottomed flask, stirring 10～36h at 120～200 DEG C, column chromatography purification obtains；Take 1mmol PXZPhBr, 5～20ml tetra-
Hydrogen furan, stirs at 0～-100 DEG C, drips 1～5mmol n-BuLi, after reaction 10～36h, adds 1～5mmol hexichol
Base phosphorus chloride stirring 5～24h, goes out reaction with shrend, adds hydrogen peroxide and stirs 1h, heavily ties through petroleum ether column chromatography, ethyl acetate
Crystalline substance, obtains thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen.
The preparation method of thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen is as follows:
Bromo-iodobenzene, 0.1～0.5mmol Hydro-Giene (Water Science)., 1～5mmol potassium carbonate are put by 1mmol phenoxazine, 1～5mmol
In round-bottomed flask, stirring 10～36h at 120～200 DEG C, column chromatography purification obtains PXZPhBr；Take 2mmol PXZPhBr, 5
～20ml oxolane, at 0～-100 DEG C stir, drip 1～10mmol n-BuLi, reaction 10～36h after, add 1～
5mmol phenyl dichloro phosphorus stirring 5～24h, goes out reaction with shrend, adds hydrogen peroxide and stirs 1h, by petroleum ether and ethyl acetate
Volume ratio is the column chromatography of 5:1, re-crystallizing in ethyl acetate, obtains thermal excitation delayed fluorescence blue light object based on triphenyl phosphorus oxygen
Material.
The preparation method of thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen is as follows:
Bromo-iodobenzene, 0.1～0.5mmol Hydro-Giene (Water Science)., 1～5mmol potassium carbonate are put by 1mmol phenoxazine, 1～5mmol
In round-bottomed flask, stirring 10～36h at 120～200 DEG C, column chromatography purification obtains PXZPhBr or PTZPhBr；Take 2mmol
PXZPhB or PTZPhBrr, 5～20ml oxolane, stirs at 0～-100 DEG C, drips 1～15mmol n-BuLi, reaction
After 10～36h, add 1～5mmol or Phosphorous chloride. phenyl dichloro phosphorus stirring 5～24h, go out reaction with shrend, addition dioxygen
Water stirring 1h, with petroleum ether with the column chromatography that ethyl acetate volume ratio is 5:1 or with petroleum ether with ethyl acetate volume ratio be
The column chromatography of 1:1, re-crystallizing in ethyl acetate, obtain thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen.
The preparation method of thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen is as follows:
Bromo-iodobenzene, 0.1～0.5mmol Hydro-Giene (Water Science)., 1～5mmol potassium carbonate are put by 1mmol phenothiazine, 1～5mmol
In round-bottomed flask, stirring 10～36h at 120～200 DEG C, column chromatography purification obtains PTZPhBr；Take 1mmol PTZPhBr, 5
～20ml oxolane, at 0～-100 DEG C stir, drip 1～5mmol n-BuLi, reaction 10～36h after, add 1～
5mmol diphenyl phosphorus chloride stirring 5～24h, goes out reaction with shrend, adds hydrogen peroxide and stirs 1h, through petroleum ether column chromatography, acetic acid
Ethyl ester recrystallization, obtains thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen.
As follows in the preparation method of thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen:
By 1mmol 9,9-dimethyl acridinium, 1～5mmol to bromo-iodobenzene, 0.1～0.5mmol Hydro-Giene (Water Science)., 1～5mmol
Potassium carbonate is placed in round-bottomed flask, stirs 10～36h at 120～200 DEG C, and column chromatography purification obtains DMACPhBr；Take 1mmol
DMACPhBr, 5～20ml, at 0～-100 DEG C stir, drip 1～5mmol n-BuLi, reaction 10～36h after, add 1～
5mmol diphenyl phosphorus chloride stirring 5～24h, goes out reaction with shrend, adds hydrogen peroxide and stirs 1h, through petroleum ether column chromatography, acetic acid
Ethyl ester recrystallization, obtains thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen.
The preparation method of thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen is as follows:
By 1mmol 9,9-dimethyl acridinium, 1～5mmol to bromo-iodobenzene, 0.1～0.5mmol Hydro-Giene (Water Science)., 1～5mmol
Potassium carbonate is placed in round-bottomed flask, stirs 10～36h at 120～200 DEG C, and column chromatography purification obtains DMACPhBr；Take 2mmol
DMACPhBr, 5～20ml oxolane, stirs at 0～-100 DEG C, drips 1～10mmol n-BuLi, reacts 10～36h
After, add 1～5mmol phenyl dichloro phosphorus stirring 5～24h, go out reaction with shrend, add hydrogen peroxide and stir 1h, use petroleum ether
It is the column chromatography of 5:1 with ethyl acetate volume ratio, re-crystallizing in ethyl acetate, obtain thermal excitation based on triphenyl phosphorus oxygen and postpone glimmering
Light blue light guest materials.
The preparation method of thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen is as follows:
By 1mmol 9,9-dimethyl acridinium, 1～5mmol to bromo-iodobenzene, 0.1～0.5mmol Hydro-Giene (Water Science)., 1～5mmol
Potassium carbonate is placed in round-bottomed flask, stirs 10～36h at 120～200 DEG C, and column chromatography purification obtains DMACPhBr；Take 3mmol
DMACPhBr, 5～20ml oxolane, stirs at 0～-100 DEG C, drips 1～15mmol n-BuLi, reacts 10～36h
After, add 1～5mmol Phosphorous chloride. stirring 5～24h, go out reaction with shrend, add hydrogen peroxide and stir 1h, by petroleum ether and second
Acetoacetic ester volume ratio is 1:1 column chromatography, re-crystallizing in ethyl acetate, obtains thermal excitation delayed fluorescence blue light based on triphenyl phosphorus oxygen
Guest materials.
Described thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen is applied to prepare thermal excitation and postpones glimmering
Light electroluminescent device.
Thermal excitation delayed fluorescence (TADF) the blue light guest materials based on triphenyl phosphorus oxygen prepared with the present invention, device bag
Including glass or plastic, be attached to the anode conductive layer in glass or plastic, material is tin indium oxide (ITO), laminating
Hole injection layer on anode conductive layer, material is MoOx, the hole transmission layer being fitted on hole injection layer, and material is
NBP, the electronic barrier layer being fitted on hole transmission layer, material is mCP, with the luminescent layer of electronic barrier layer laminating, luminescent layer
Material of main part is DPEPO, and guest materials is thermal excitation delayed fluorescence (TADF) blue light based on phenyl phosphorus oxygen proposed in patent
Guest materials, with the hole blocking layer of luminescent layer laminating, material DPEPO, with the electron transfer layer of hole blocking layer laminating, material
For Bphen, with the electron injecting layer of electron transfer layer laminating, material is LiF, the cathode conductive layer fitted with electron injecting layer,
Material is metal Al；The most each layer thickness is respectively: tin indium oxide thickness is 100nm；MoOx thickness is 10nm；NPB thickness is
50nm；MCP thickness is 15nm；Light emitting layer thickness is 30nm, and the doping content of object is 20%；DPEPO thickness is 20nm；
Bphen thickness is 50nm；LiF thickness is 0.5nm；Metal Al thickness is 150nm.
The present invention is using weak electronic donor group as the donor in molecular structure, using triphenylphosphine oxide as molecular structure
In receptor, make donor and receptor combine by the reaction such as ullmann reaction and halogen lithium, synthesize multiple TADF dyestuff.The present invention with
Triphenylphosphine oxide is receptor, utilizes the electron donor such as phenothiazine, phenoxazine to carry out short axle modification, constructs acceptor-donor (D-A) type
Molecule, synthesizes TADF dyestuff, it is achieved the most blue coloured electroluminous.Utilize weak electron-withdrawing of triphenylphosphine oxide, and to electronics
Group forms weak electron donor-acceptor structure, the distorted-structure in space, it is possible to the injection of balancing charge and transmission, gives electricity by regulation and control
Subbase group, it is achieved efficient electroluminescent photoluminescence.
Present invention thermal excitation based on triphenyl phosphorus oxygen delayed fluorescence (TADF) blue light guest materials is used for electroluminescent cell
Part comprises advantages below:
1, modify, due to short axle, the triplet making material of main part holding higher.
2, the weak electron-withdrawing power utilizing phosphine oxygen groups reduces lumo energy, and the electronics that improve material injects and transmission
Ability.The D-A system constructed by phosphine oxygen groups and weak electron donor can the injection of equilbrium carrier and transmission.
Accompanying drawing explanation
Fig. 1 is the SPXZPPO Ultraluminescence spectrum spectrogram of embodiment one synthesis, wherein represents SPXZPPO/ bis-with ■ curve
The uv absorption spectra of chloromethanes, use ▲ curve represents the fluorescence emission spectrogram of SPXZPPO/ dichloromethane；
Fig. 2 is the thermogravimetric analysis spectrogram of the SPXZPPO of embodiment one synthesis；
Fig. 3 is the DPXZPPO Ultraluminescence spectrum spectrogram of embodiment two synthesis, wherein represents DPXZPPO/ bis-with ■ curve
The uv absorption spectra of chloromethanes, use ▲ curve represents the fluorescence emission spectrogram of DPXZPPO/ dichloromethane；
Fig. 4 is the thermogravimetric analysis spectrogram of the DPXZPPO of embodiment two synthesis；
Fig. 5 is the TPXZPPO Ultraluminescence spectrum spectrogram of embodiment three synthesis, wherein represents TPXZPPO/ bis-with ■ curve
The uv absorption spectra of chloromethanes, use ▲ curve represents the fluorescence emission spectrogram of TPXZPPO/ dichloromethane；
Fig. 6 is the thermogravimetric analysis spectrogram of the TPXZPPO of embodiment three synthesis；
Fig. 7 is the SPTZPPO Ultraluminescence spectrum spectrogram of embodiment four synthesis, wherein represents SPTZPPO/ bis-with ■ curve
The uv absorption spectra of chloromethanes, use ▲ curve represents the fluorescence emission spectrogram of SPXZPPO/ dichloromethane；
Fig. 8 is the thermogravimetric analysis spectrogram of the SPTTPPO of embodiment four synthesis；
Fig. 9 is the DPTZPPO Ultraluminescence spectrum spectrogram of embodiment five synthesis, wherein represents DPTZPPO/ bis-with ■ curve
The uv absorption spectra of chloromethanes, use ▲ curve represents the fluorescence emission spectrogram of DPTZPPO/ dichloromethane；
Figure 10 is the thermogravimetric analysis spectrogram of the DPTZPPO of embodiment five synthesis；
Figure 11 is the TPTZPPO Ultraluminescence spectrum spectrogram that the embodiment six directions becomes, and wherein represents TPTZPPO/ with ■ curve
The uv absorption spectra of dichloromethane, use ▲ curve represents the fluorescence emission spectrogram of TPTZPPO/ dichloromethane；
Figure 12 is the thermogravimetric analysis spectrogram of the TPTZPPO that the embodiment six directions becomes；
Figure 13 is that the blue fever of embodiment seven to embodiment nine preparation excites the voltage-current density of delayed fluorescence device to close
It is curve, wherein represents SPXZPPO with ■, use ● represent DPXZPPO, with ▲ represent TPXZPPO, with representing SPTZPPO, use
◆ represent DPTZPPO, useRepresent TPTZPPO；
Figure 14 is the voltage-brightness relation song that blue fever prepared by embodiment seven to embodiment nine excites delayed fluorescence device
Line, wherein represents SPXZPPO with ■, uses ● represent DPXZPPO, with ▲ represent TPXZPPO, with representing SPTZPPO, use ◆ table
Show DPTZPPO, useRepresent TPTZPPO；
Figure 15 is that the blue fever of embodiment seven to embodiment nine preparation excites the luminance-current efficiency of delayed fluorescence device to close
It is curve, wherein represents SPXZPPO with ■, use ● represent DPXZPPO, with ▲ represent TPXZPPO, with representing SPTZPPO, use
◆ represent DPTZPPO, useRepresent TPTZPPO；
Figure 16 is that the blue fever of embodiment seven to embodiment nine preparation excites the brightness-power efficiency of delayed fluorescence device to close
It is curve, wherein represents SPXZPPO with ■, use ● represent DPXZPPO, with ▲ represent TPXZPPO, with representing SPTZPPO, use
◆ represent DPTZPPO, useRepresent TPTZPPO；
Figure 17 is brightness-external quantum efficiency that blue fever prepared by embodiment seven to embodiment nine excites delayed fluorescence device
Relation curve, wherein represents SPXZPPO with ■, uses ● represent DPXZPPO, with ▲ represent TPXZPPO, with representing SPTZPPO,
With ◆ represent DPTZPPO, useRepresent TPTZPPO；
Figure 18 is the electroluminescent spectrum that blue fever prepared by embodiment seven to embodiment nine excites delayed fluorescence device, its
Middle ■ represents SPXZPPO, uses ● represent DPXZPPO, with ▲ represent TPXZPPO, with representing SPTZPPO, use ◆ represent
DPTZPPO, usesRepresent TPTZPPO.
Detailed description of the invention
Technical solution of the present invention is not limited to act detailed description of the invention set forth below, also includes between each detailed description of the invention
Combination in any.
Detailed description of the invention one: thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen in present embodiment
Structural formula as follows:
Wherein R group isX is
Detailed description of the invention two: thermal excitation delayed fluorescence blue light based on triphenyl phosphorus oxygen visitor described in detailed description of the invention one
The preparation method of body material is as follows:
Bromo-iodobenzene, 0.1～0.5mmol Hydro-Giene (Water Science)., 1～5mmol potassium carbonate are put by 1mmol phenoxazine, 1～5mmol
In round-bottomed flask, stirring 10～36h at 120～200 DEG C, column chromatography purification obtains PXZPhBr；Take 1mmol PXZPhBr, 5
～20ml oxolane, at 0～-100 DEG C stir, drip 1～5mmol n-BuLi, reaction 10～36h after, add 1～
5mmol diphenyl phosphorus chloride stirring 5～24h, goes out reaction with shrend, adds hydrogen peroxide and stirs 1h, through petroleum ether column chromatography, acetic acid
Ethyl ester recrystallization, obtains thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen.
Detailed description of the invention three: thermal excitation delayed fluorescence blue light based on triphenyl phosphorus oxygen visitor described in detailed description of the invention one
The preparation method of body material is as follows:
Bromo-iodobenzene, 0.1～0.5mmol Hydro-Giene (Water Science)., 1～5mmol potassium carbonate are put by 1mmol phenoxazine, 1～5mmol
In round-bottomed flask, stirring 10～36h at 120～200 DEG C, column chromatography purification obtains PXZPhBr or PTZPhBr；Take 2mmol
PXZPhB or PTZPhBrr, 5～20ml oxolane, stirs at 0～-100 DEG C, drips 1～15mmol n-BuLi, reaction
After 10～36h, add 1～5mmol or Phosphorous chloride. phenyl dichloro phosphorus stirring 5～24h, go out reaction with shrend, addition dioxygen
Water stirring 1h, with petroleum ether with the column chromatography that ethyl acetate volume ratio is 5:1 or with petroleum ether with ethyl acetate volume ratio be
The column chromatography of 1:1, re-crystallizing in ethyl acetate, obtain thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen.
Detailed description of the invention four: thermal excitation delayed fluorescence blue light based on triphenyl phosphorus oxygen visitor described in detailed description of the invention one
The preparation method of body material is as follows:
Bromo-iodobenzene, 0.1～0.5mmol Hydro-Giene (Water Science)., 1～5mmol potassium carbonate are put by 1mmol phenoxazine, 1～5mmol
In round-bottomed flask, stirring 10～36h at 120～200 DEG C, column chromatography purification obtains PXZPhBr；Take 3mmol PXZPhBr, 5
～20ml oxolane, at 0～-100 DEG C stir, drip 1～15mmol n-BuLi, reaction 10～36h after, add 1～
5mmol Phosphorous chloride. stirring 5～24h, goes out reaction with shrend, adds hydrogen peroxide stirring 1h, with petroleum ether and ethyl acetate volume
Than the column chromatography for 1:1, re-crystallizing in ethyl acetate, obtain thermal excitation delayed fluorescence blue light object material based on triphenyl phosphorus oxygen
Material.
Detailed description of the invention five: thermal excitation delayed fluorescence blue light based on triphenyl phosphorus oxygen visitor described in detailed description of the invention one
The preparation method of body material is as follows:
Bromo-iodobenzene, 0.1～0.5mmol Hydro-Giene (Water Science)., 1～5mmol potassium carbonate are put by 1mmol phenothiazine, 1～5mmol
In round-bottomed flask, stirring 10～36h at 120～200 DEG C, column chromatography purification obtains PTZPhBr；Take 1mmol PTZPhBr, 5
～20ml oxolane, at 0～-100 DEG C stir, drip 1～5mmol n-BuLi, reaction 10～36h after, add 1～
5mmol diphenyl phosphorus chloride stirring 5～24h, goes out reaction with shrend, adds hydrogen peroxide and stirs 1h, through petroleum ether column chromatography, acetic acid
Ethyl ester recrystallization, obtains thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen.
Detailed description of the invention six: thermal excitation delayed fluorescence blue light based on triphenyl phosphorus oxygen visitor described in detailed description of the invention one
The preparation method of body material is as follows:
By 1mmol 9,9-dimethyl acridinium, 1～5mmol to bromo-iodobenzene, 0.1～0.5mmol Hydro-Giene (Water Science)., 1～5mmol
Potassium carbonate is placed in round-bottomed flask, stirs 10～36h at 120～200 DEG C, and column chromatography purification obtains DMACPhBr；Take 1mmol
DMACPhBr, 5～20ml oxolane, stirs at 0～-100 DEG C, drips 1～5mmol n-BuLi, reacts 10～36h
After, add 1～5mmol diphenyl phosphorus chloride stirring 5～24h, go out reaction with shrend, add hydrogen peroxide and stir 1h, through petroleum ether
Column chromatography, re-crystallizing in ethyl acetate, obtain thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen.
Detailed description of the invention seven: thermal excitation delayed fluorescence blue light based on triphenyl phosphorus oxygen visitor described in detailed description of the invention one
The preparation method of body material is as follows:
By 1mmol 9,9-dimethyl acridinium, 1～5mmol to bromo-iodobenzene, 0.1～0.5mmol Hydro-Giene (Water Science)., 1～5mmol
Potassium carbonate is placed in round-bottomed flask, stirs 10～36h at 120～200 DEG C, and column chromatography purification obtains DMACPhBr；Take 2mmol
DMACPhBr, 5～20ml oxolane, stirs at 0～-100 DEG C, drips 1～10mmol n-BuLi, reacts 10～36h
After, add 1～5mmol phenyl dichloro phosphorus stirring 5～24h, go out reaction with shrend, add hydrogen peroxide and stir 1h, use petroleum ether
It is the column chromatography of 5:1 with ethyl acetate volume ratio, re-crystallizing in ethyl acetate, obtain thermal excitation based on triphenyl phosphorus oxygen and postpone glimmering
Light blue light guest materials.
Detailed description of the invention eight: thermal excitation delayed fluorescence blue light based on triphenyl phosphorus oxygen visitor described in detailed description of the invention one
The preparation method of body material is as follows:
By 1mmol 9,9-dimethyl acridinium, 1～5mmol to bromo-iodobenzene, 0.1～0.5mmol Hydro-Giene (Water Science)., 1～5mmol
Potassium carbonate is placed in round-bottomed flask, stirs 10～36h at 120～200 DEG C, and column chromatography purification obtains DMACPhBr；Take 3mmol
DMACPhBr, 5～20ml oxolane, stirs at 0～-100 DEG C, drips 1～15mmol n-BuLi, reacts 10～36h
After, add 1～5mmol Phosphorous chloride. stirring 5～24h, go out reaction with shrend, add hydrogen peroxide and stir 1h, by petroleum ether and second
Acetoacetic ester volume ratio is 1:1 column chromatography, re-crystallizing in ethyl acetate, obtains thermal excitation delayed fluorescence blue light based on triphenyl phosphorus oxygen
Guest materials.
Detailed description of the invention nine: thermal excitation delayed fluorescence blue light based on triphenyl phosphorus oxygen visitor described in detailed description of the invention one
Body materials application is in preparation thermal excitation delayed fluorescence electroluminescent device.
Thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen is applied to prepare thermal excitation delayed fluorescence electricity
The method of electroluminescence device is as follows:
One, the glass cleaned through deionized water or plastic are put into vacuum evaporation instrument, be 1 × 10 in vacuum- 6Mbar, evaporation rate are 0.1nm s-1Under conditions of, glass or plastic are deposited with tin indium oxide, obtaining thickness is
The anode conductive layer of 100nm；
Two, on anode conductive layer, it is deposited with MoOx, obtains the hole injection layer that thickness is 10nm；
Three, on hole injection layer, it is deposited with NPB, obtains the hole transmission layer that thickness is 50nm；
Four, on hole transmission layer, it is deposited with mCP, obtains the electronic barrier layer that thickness is 15nm；
Five, continuing evaporation thickness on electronic barrier layer is that (thermal excitation of triphenyl phosphorus oxygen postpones 30nm subject and object
Fluorescent guest material) luminescent layer that adulterates, the doping content (quality) of object is 20%；
Six, on luminescent layer, it is deposited with DPEPO, obtains the hole blocking layer that thickness is 20nm；
Seven, being deposited with Bphen on hole blocking layer, thickness degree of obtaining is the electron transfer layer of 50nm；
Eight, it is deposited with LiF on the electron transport layer, obtains the electron injecting layer that thickness is 0.5nm；
Nine, evaporation metal Al on electron injecting layer, thickness is the cathode conductive layer of 150nm, encapsulation, obtains thermal excitation and prolongs
Fluorescence (TADF) electroluminescent device late.
Use following embodiment verify effect of the present invention:
Embodiment one: the present embodiment thermal excitation based on triphenyl phosphorus oxygen delayed fluorescence (TADF) blue light guest materials
(SPXZPPO) synthetic method follows these steps to realize:
One, bromo-iodobenzene, 0.02mmol Hydro-Giene (Water Science)., 1mmol potassium carbonate are placed in through overbaking by 1mmol phenoxazine, 1mmol
In the roasting 50ml three neck round bottom except water, stirring 12h under argon shield at 140 DEG C, stopping reacting by heating recovery room temperature will
Reactant mixture washes with water three times, then extracts with dichloromethane, organic layer anhydrous Na SO4Being dried, vacuum rotary steam is gone out molten
Agent, goes out product and obtains 10-(4-bromophenyl)-10 hydrogen-phenoxazine through column chromatography purification.
Two, take 1mmol 10-(4-bromophenyl)-10 hydrogen-phenoxazine, 20ml oxolane, be placed in toasted except water
In 50ml three neck round bottom, stir at being cooled to-40 DEG C with liquid nitrogen and alcohol mixture, whipping process is slowly added dropwise
1mmol n-BuLi, after reaction 12h, is slowly added dropwise 1mmol diphenyl phosphorus chloride stirring 12h, goes out reaction with shrend, adds pair
Oxygen water stirring 1h, extracts with dichloromethane, organic layer anhydrous Na SO4Being dried, vacuum rotary steam goes out solvent, and thick product is through post layer
Analysis purification, re-crystallizing in ethyl acetate obtains (4-(10 hydrogen phenoxazine-10-base) phenyl) diphenylphosphine oxygen (SPXZPPO).
The structural formula of SPXZPPO is as follows:
10-(4-bromophenyl)-10 hydrogen-phenoxazine of the present embodiment step one preparation, the data of its proton nmr spectra are
:1H NMR(TMS,CDCl3, 400MHz): δ=7.986-7.967 (d, J=7.6Hz, 1H), 7.786-7.767 (d, J=
7.6Hz, 1H), 7.307 (d, 1H), 7.165-7.146 (d, J=7.6Hz, 1H), 6.754-6.534 (m, 6H), 5.977-
5.958ppm (d, J=7.6Hz, 2H).
SPXZPPO prepared by the present embodiment step 2, the data of its proton nmr spectra are: N1H NMR(TMS,CDCl3,
400MHz): δ=7.907-7.859 (dd, J=8.0,8.4Hz, 2H), 7.771-7.720 (m, 4H), 7.616-7.576 (m, J
=1.2,1.2,1.6Hz, 2H), 7.544-7.500 (m, 4H), 7.469-7.453 (d, J=6.4Hz, 2H), 6.707-6.705
(m, J=6.4,7.6Hz, 6H), 5.938-5.925ppm (t, J=2.8,2.4Hz, 2H).
The present embodiment obtains the present embodiment thermal excitation based on triphenyl phosphorus oxygen delayed fluorescence (TADF) blue light guest materials
The Ultraluminescence spectrum spectrogram of SPXZPPO is as shown in Figure 1.
The present embodiment obtains the present embodiment thermal excitation based on triphenyl phosphorus oxygen delayed fluorescence (TADF) blue light guest materials
The thermogravimetric analysis spectrogram of SPXZPPO is as in figure 2 it is shown, the present embodiment thermal excitation based on triphenyl phosphorus oxygen delayed fluorescence as seen from the figure
(TADF) cracking temperature of blue light guest materials SPXZPPO reaches 372 DEG C.
Embodiment two: the present embodiment thermal excitation based on triphenyl phosphorus oxygen delayed fluorescence (TADF) blue light guest materials
(DPXZPPO) synthetic method follows these steps to realize:
Bromo-iodobenzene, 0.02mmol Hydro-Giene (Water Science)., 1mmol potassium carbonate are placed in through overbaking by 1mmol phenoxazine, 1mmol
Except, in the 50ml three neck round bottom of water, stirring 12h under argon shield at 140 DEG C, stop reacting by heating and recover room temperature by anti-
Answer mixture to wash with water three times, then extract with dichloromethane, organic layer anhydrous Na SO4Being dried, vacuum rotary steam goes out solvent,
Go out product and obtain PXZPhBr through column chromatography purification.Take 2mmol PXZPhBr, 20ml oxolane, be placed in toasted except water
In 50ml three neck round bottom, stir at being cooled to-40 DEG C with liquid nitrogen and alcohol mixture, whipping process is slowly added dropwise
2mmol n-BuLi, after reaction 12h, is slowly added dropwise 1mmol phenyl dichloro phosphorus stirring 12h, goes out reaction with shrend, adds pair
Oxygen water stirring 1h, extracts with dichloromethane, organic layer anhydrous Na SO4Being dried, vacuum rotary steam goes out solvent, and thick product is through post layer
Analysis purification, re-crystallizing in ethyl acetate obtains DPXZPPO.
The structural formula of DPXZPPO is as follows:
The nuclear-magnetism of the present embodiment thermal excitation based on triphenyl phosphorus oxygen delayed fluorescence (TADF) blue light guest materials DPXZPPO
Resonance hydrogen modal data is:1H NMR(TMS,CDCl3, 400MHz): δ=7.982-7.933 (dd, J=8.0,8.4Hz, 4H),
7.851-7.803 (m, 2H), 7.659-7.638 (dd, J=8.0,8.0Hz, 1H), 7.614-7.570 (m, 2H), 7.544-
7.519 (dd, J=2.0,2.0Hz, 4H), 6.72-6.606 (m, 12H), 5.977-5.958ppm (d, J=7.6Hz, 4H).
The present embodiment obtains the present embodiment thermal excitation based on triphenyl phosphorus oxygen delayed fluorescence (TADF) blue light guest materials
The Ultraluminescence spectrum spectrogram of DPXZPPO is as shown in Figure 3.
The present embodiment obtains thermal excitation delayed fluorescence (TADF) blue light guest materials DPXZPPO's based on triphenyl phosphorus oxygen
Thermogravimetric analysis spectrogram as shown in Figure 4, thermal excitation delayed fluorescence (TADF) blue light object material based on triphenyl phosphorus oxygen as seen from the figure
The cracking temperature of material DPXZPPO reaches 442 DEG C.
Embodiment three: thermal excitation delayed fluorescence (TADF) blue light guest materials (TPXZPPO) based on triphenyl phosphorus oxygen
Synthetic method:
Bromo-iodobenzene, 0.02mmol Hydro-Giene (Water Science)., 1mmol potassium carbonate are placed in through overbaking by 1mmol phenoxazine, 1mmol
Except, in the 50ml three neck round bottom of water, stirring 12h under argon shield at 140 DEG C, stop reacting by heating and recover room temperature by anti-
Answer mixture to wash with water three times, then extract with dichloromethane, organic layer anhydrous Na SO4Being dried, vacuum rotary steam goes out solvent,
Go out product and obtain PXZPhBr through column chromatography purification.Take 3mmol PXZPhBr, 20ml oxolane, be placed in toasted except water
In 50ml three neck round bottom, stir at being cooled to-40 DEG C with liquid nitrogen and alcohol mixture, whipping process is slowly added dropwise
3mmol n-BuLi, after reaction 12h, is slowly added dropwise 1mmol Phosphorous chloride. stirring 12h, goes out reaction with shrend, addition hydrogen peroxide
Stirring 1h, extracts with dichloromethane, organic layer anhydrous Na SO4Being dried, vacuum rotary steam goes out solvent, and thick product is pure through column chromatography
Changing, re-crystallizing in ethyl acetate obtains TPXZPPO.
The structural formula of TPXZPPO is as follows:
The nuclear-magnetism of the present embodiment thermal excitation based on triphenyl phosphorus oxygen delayed fluorescence (TADF) blue light guest materials TPXZPPO
Resonance hydrogen modal data is:1H NMR(TMS,CDCl3, 400MHz): δ=8.050-8.001 (dd, J=8.0,8.0Hz, 6H),
7.612-7.591 (t, J=2.0,6.4Hz, 6H), 6.747-6.624 (m, 18H), 6.018-5.999ppm (d, J=7.6Hz,
6H).
The present embodiment obtains thermal excitation delayed fluorescence (TADF) blue light guest materials TPXZPPO's based on triphenyl phosphorus oxygen
Ultraluminescence spectrum spectrogram is as shown in Figure 5.
The present embodiment obtains thermal excitation delayed fluorescence (TADF) blue light guest materials TPXZPPO's based on triphenyl phosphorus oxygen
Thermogravimetric analysis spectrogram as shown in Figure 6, thermal excitation delayed fluorescence (TADF) blue light object material based on triphenyl phosphorus oxygen as seen from the figure
The cracking temperature of material TPXZPPO reaches 465 DEG C.
Embodiment four: the present embodiment thermal excitation based on triphenyl phosphorus oxygen delayed fluorescence (TADF) blue light guest materials
The synthetic method of SPTZPPO follows these steps to realize:
One, bromo-iodobenzene, 0.02mmol Hydro-Giene (Water Science)., 1mmol potassium carbonate are placed in through overbaking by 1mmol phenothiazine, 1mmol
In the roasting 50ml three neck round bottom except water, stirring 12h under argon shield at 140 DEG C, stopping reacting by heating recovery room temperature will
Reactant mixture washes with water three times, then extracts with dichloromethane, organic layer anhydrous Na SO4Being dried, vacuum rotary steam is gone out molten
Agent, goes out product and obtains 10-(4-bromophenyl)-10 hydrogen-phenothiazine through column chromatography purification.
Two, take 1mmol 10-(4-bromophenyl)-10 hydrogen-phenothiazine, 20ml oxolane, be placed in toasted except water
In 50ml three neck round bottom, stir at being cooled to-40 DEG C with liquid nitrogen and alcohol mixture, whipping process is slowly added dropwise
1mmol n-BuLi, after reaction 12h, is slowly added dropwise 1mmol diphenyl phosphorus chloride stirring 12h, goes out reaction with shrend, adds pair
Oxygen water stirring 1h, extracts with dichloromethane, organic layer anhydrous Na SO4Being dried, vacuum rotary steam goes out solvent, and thick product is through post layer
Analysis purification, re-crystallizing in ethyl acetate obtains (4-(10 hydrogen phenoxazine-10-base) phenyl) diphenylphosphine oxygen (SPTZPPO).
The structural formula of SPTZPPO is as follows:
10-(4-bromophenyl)-10 hydrogen-phenothiazine of the present embodiment step one preparation, the data of its proton nmr spectra are
:1H NMR(TMS,CDCl3, 400MHz): δ=7.747-7.726 (d, J=8.8Hz, 2H), 7.310-7.284 (d, J=
7.6Hz, 2H), 7.089-7.066 (dd, J=1.6Hz, 2.0Hz, 2H), 6.931-6.897 (m, 4H), 6.288-6.268ppm
(d, J=8Hz, 2H).
SPTZPPO prepared by the present embodiment step 2, the data of its proton nmr spectra are: N1H NMR(TMS,CDCl3,
400MHz): δ=7.772-7.724 (dd, J=8.0Hz, 8.8Hz, 4H), 7.694-7.646 (t, J=10.0Hz, 9.2Hz,
2H), 7.605-7.569 (t, J=14.4Hz, 7.2Hz, 4H), 7.331-7.279 (t, 4H), 7.196-7.159 (t, J=
7.2Hz, 7.6Hz, 2H), 7.108-7.072 (t, J=7.2Hz, 7.2Hz, 2H), 6.968-6.948ppm (d, J=8Hz, 2H).
The present embodiment obtains the present embodiment thermal excitation based on triphenyl phosphorus oxygen delayed fluorescence (TADF) blue light guest materials
The Ultraluminescence spectrum spectrogram of SPTZPPO is as shown in Figure 7.
The present embodiment obtains the present embodiment thermal excitation based on triphenyl phosphorus oxygen delayed fluorescence (TADF) blue light guest materials
The thermogravimetric analysis spectrogram of SPTZPPO as shown in Figure 8, the present embodiment thermal excitation based on triphenyl phosphorus oxygen delayed fluorescence as seen from the figure
(TADF) cracking temperature of blue light guest materials SPTZPPO reaches 389 DEG C.
Embodiment five: the present embodiment thermal excitation based on triphenyl phosphorus oxygen delayed fluorescence (TADF) blue light guest materials
The synthetic method of DPTZPPO follows these steps to realize:
Bromo-iodobenzene, 0.02mmol Hydro-Giene (Water Science)., 1mmol potassium carbonate are placed in through overbaking by 1mmol phenothiazine, 1mmol
Except, in the 50ml three neck round bottom of water, stirring 12h under argon shield at 140 DEG C, stop reacting by heating and recover room temperature by anti-
Answer mixture to wash with water three times, then extract with dichloromethane, organic layer anhydrous Na SO4Being dried, vacuum rotary steam goes out solvent,
Go out product and obtain PTZPhBr through column chromatography purification.Take 2mmol PTZPhBr, 20ml oxolane, be placed in toasted except water
In 50ml three neck round bottom, stir at being cooled to-40 DEG C with liquid nitrogen and alcohol mixture, whipping process is slowly added dropwise
2mmol n-BuLi, after reaction 12h, is slowly added dropwise 1mmol phenyl dichloro phosphorus stirring 12h, goes out reaction with shrend, adds pair
Oxygen water stirring 1h, extracts with dichloromethane, organic layer anhydrous Na SO4Being dried, vacuum rotary steam goes out solvent, and thick product is through post layer
Analysis purification, re-crystallizing in ethyl acetate obtains DPTZPPO.
The structural formula of DPTZPPO is as follows:
The nuclear-magnetism of the present embodiment thermal excitation based on triphenyl phosphorus oxygen delayed fluorescence (TADF) blue light guest materials DPTZPPO
Resonance hydrogen modal data is:1H NMR(TMS,CDCl3, 400MHz): δ=7.798-7.749 (dd, J=8.4Hz, 9.2Hz, 2H),
7.721-7.673 (t, J=10Hz, 9.2Hz, 4Hz), 7.611-7.575 (t, J=6.8Hz, 0.8Hz, 1H), 7.539-7.503
(t, J=7.2Hz, 0.8Hz, 2H), 7.336-7.311 (d, J=10Hz, 8Hz), 7.201-7.164 (t, J=7.2Hz,
7.6Hz, 4H), 7.115-7.078 (t, J=7.6Hz, 7.2Hz, 4H), 6.971-6.951ppm (d, J=8Hz, 4H).
The present embodiment obtains thermal excitation delayed fluorescence (TADF) blue light guest materials DPTZPPO's based on triphenyl phosphorus oxygen
Ultraluminescence spectrum spectrogram is as shown in Figure 9.
The present embodiment obtains thermal excitation delayed fluorescence (TADF) blue light guest materials DPTZPPO's based on triphenyl phosphorus oxygen
Thermogravimetric analysis spectrogram as shown in Figure 10, thermal excitation delayed fluorescence (TADF) blue light object material based on triphenyl phosphorus oxygen as seen from the figure
The cracking temperature of material DPTZPPO reaches 386 DEG C.
Embodiment six: the conjunction of thermal excitation delayed fluorescence (TADF) blue light guest materials TPTZPPO based on triphenyl phosphorus oxygen
One-tenth method:
Bromo-iodobenzene, 0.02mmol Hydro-Giene (Water Science)., 1mmol potassium carbonate are placed in through overbaking by 1mmol phenothiazine, 1mmol
Except, in the 50ml three neck round bottom of water, stirring 12h under argon shield at 140 DEG C, stop reacting by heating and recover room temperature by anti-
Answer mixture to wash with water three times, then extract with dichloromethane, organic layer anhydrous Na SO4Being dried, vacuum rotary steam goes out solvent,
Go out product and obtain PTZPhBr through column chromatography purification.Take 3mmol PTZPhBr, 20ml oxolane, be placed in toasted except water
In 50ml three neck round bottom, stir at being cooled to-40 DEG C with liquid nitrogen and alcohol mixture, whipping process is slowly added dropwise
3mmol n-BuLi, after reaction 12h, is slowly added dropwise 1mmol Phosphorous chloride. stirring 12h, goes out reaction with shrend, addition hydrogen peroxide
Stirring 1h, extracts with dichloromethane, organic layer anhydrous Na SO4Being dried, vacuum rotary steam goes out solvent, and thick product is pure through column chromatography
Changing, re-crystallizing in ethyl acetate obtains TPTZPPO.
The structural formula of TPTZPPO is as follows:
The nuclear-magnetism of the present embodiment thermal excitation based on triphenyl phosphorus oxygen delayed fluorescence (TADF) blue light guest materials TPTZPPO
Resonance hydrogen modal data is:1H NMR(TMS,CDCl3, 400MHz): δ=7.721-7.671 (dd, J=11.2Hz, 8.4Hz,
8.8Hz), 7.311-7.261 (m, 12), 7.176-7.134 (ddd, J=1.2Hz, 1.2Hz, 1.6Hz), 7.090-7.050
(ddd, J=1.2Hz, 0.8Hz, 1.2Hz), 6.944-6.921ppm (dd, J=1.2Hz, 1.2Hz).
The present embodiment obtains thermal excitation delayed fluorescence (TADF) blue light guest materials TPTZPPO's based on triphenyl phosphorus oxygen
Ultraluminescence spectrum spectrogram is as shown in figure 11.
The present embodiment obtains thermal excitation delayed fluorescence (TADF) blue light guest materials TPXZPPO's based on triphenyl phosphorus oxygen
Thermogravimetric analysis spectrogram as shown in figure 12, thermal excitation delayed fluorescence (TADF) blue light object material based on triphenyl phosphorus oxygen as seen from the figure
The cracking temperature of material TPTZPPO reaches 407 DEG C.
Embodiment seven: the present embodiment thermal excitation based on triphenyl phosphorus oxygen delayed fluorescence (TADF) blue light guest materials
The blue light electroluminescence phosphorescent devices of SPXZPPO is prepared according to the following steps:
One, the glass cleaned through deionized water or plastic being put into vacuum evaporation instrument, vacuum is 1 × 10- 6Mbar, evaporation rate is set to 0.1nm s-1, glass or plastic are deposited with tin indium oxide, obtain the sun that thickness is 100nm
Pole conductive layer；
Two, on anode conductive layer, it is deposited with MoOx, obtains the hole injection layer that thickness is 10nm；
Three, on hole injection layer, it is deposited with NPB, obtains the hole transmission layer that thickness is 50nm；
Four, on hole transmission layer, it is deposited with mCP, obtains the electronic barrier layer that thickness is 15nm；
Five, continuing evaporation thickness on electronic barrier layer, to be that 30nm main body and thermal excitation based on triphenyl phosphorus oxygen postpone glimmering
The luminescent layer of light (TADF) blue light guest materials SPXZPPO doping, the doping content (quality) of object is 20%；
Six, on luminescent layer, it is deposited with DPEPO, obtains the hole blocking layer that thickness is 20nm；
Seven, on hole blocking layer, it is deposited with Bphen, obtains the electron transfer layer that thickness is 50nm；
Eight, it is deposited with LiF on the electron transport layer, obtains the electron injecting layer that thickness is 0.5nm；
Nine, evaporation metal Al on electron injecting layer, obtains the cathode conductive layer that thickness is 150nm, encapsulation, obtains heat shock
Send out delayed fluorescence (TADF) electroluminescent device.
The structure of the present embodiment electro phosphorescent device is: ITO/MoO3(10nm)/NPB(50nm)/mCP(15nm)/
DPEPO:SPXZPPO (20%, 30nm)/DPEPO (20nm)/Bphen (50nm)/LiF (0.5nm)/Al (150nm).
The present embodiment is prepared with thermal excitation delayed fluorescence (TADF) blue light guest materials SPXZPPO based on triphenyl phosphorus oxygen
Electro phosphorescent device voltage-current density relation curve as shown in figure 13.
The preparation of the present embodiment thermal excitation based on triphenyl phosphorus oxygen delayed fluorescence (TADF) blue light guest materials SPXZPPO
Blue light electroluminescence phosphorescent devices voltage-brightness relation curve as shown in figure 14, thus figure understand this device the bright voltage that opens be
4.4V。
The present embodiment is with the system of thermal excitation delayed fluorescence (TADF) blue light guest materials SPXZPPO based on triphenyl phosphorus oxygen
As shown in figure 15, thus figure understands this device current effect to the luminance-current efficiency relation curve of standby blue light electroluminescence phosphorescent devices
Rate reaches maximum 6.5cd A-1。
The present embodiment is with the system of thermal excitation delayed fluorescence (TADF) blue light guest materials SPXZPPO based on triphenyl phosphorus oxygen
As shown in figure 16, thus figure understands this device power effect to the brightness of standby blue light electroluminescence phosphorescent devices-power efficiency relation curve
Rate reaches maximum 4.0lm W-1。
The present embodiment is with the system of thermal excitation delayed fluorescence (TADF) blue light guest materials SPXZPPO based on triphenyl phosphorus oxygen
As shown in figure 17, thus figure understands this device maximum to the brightness of standby blue light electroluminescence phosphorescent devices-external quantum efficiency relation curve
External quantum efficiency 5%.
The present embodiment is with the system of thermal excitation delayed fluorescence (TADF) blue light guest materials SPXZPPO based on triphenyl phosphorus oxygen
As shown in figure 18, thus the electroluminescent peak of this device knowable to figure exists the electroluminescent light spectrogram of standby blue light electroluminescence phosphorescent devices
At 448nm.
Embodiment eight: the present embodiment thermal excitation based on triphenyl phosphorus oxygen delayed fluorescence (TADF) blue light guest materials
The blue light electroluminescence phosphorescent devices of DPXZPPO is prepared according to the following steps:
One, the glass cleaned through deionized water or plastic being put into vacuum evaporation instrument, vacuum is 1 × 10- 6Mbar, evaporation rate is set to 0.1nm s-1, glass or plastic are deposited with tin indium oxide, obtain the sun that thickness is 100nm
Pole conductive layer；
Two, on anode conductive layer, it is deposited with MoOx, obtains the hole injection layer that thickness is 10nm；
Three, on hole injection layer, it is deposited with NPB, obtains the hole transmission layer that thickness is 50nm；
Four, on hole transmission layer, it is deposited with mCP, obtains the electronic barrier layer that thickness is 15nm；
Five, continuing evaporation thickness on electronic barrier layer, to be that 30nm main body and thermal excitation based on triphenyl phosphorus oxygen postpone glimmering
The luminescent layer of light (TADF) blue light guest materials DPXZPPO doping, the doping content (quality) of object is 20%；
Six, on luminescent layer, it is deposited with DPEPO, obtains the hole blocking layer that thickness is 20nm；
Seven, on hole blocking layer, it is deposited with Bphen, obtains the electron transfer layer that thickness is 50nm；
Eight, it is deposited with LiF on the electron transport layer, obtains the electron injecting layer that thickness is 0.5nm；
Nine, evaporation metal Al on electron injecting layer, obtains the cathode conductive layer that thickness is 150nm, encapsulation, obtains heat shock
Send out delayed fluorescence (TADF) electroluminescent device.
The structure of the present embodiment electro phosphorescent device is: ITO/MoO3(10nm)/NPB(50nm)/mCP(15nm)/
DPEPO:DPXZPPO (20%, 30nm)/DPEPO (20nm)/Bphen (50nm)/LiF (0.5nm)/Al (150nm).
The present embodiment is prepared with thermal excitation delayed fluorescence (TADF) blue light guest materials DPXZPPO based on triphenyl phosphorus oxygen
Electro phosphorescent device voltage-current density relation curve as shown in figure 13.
The preparation of the present embodiment thermal excitation based on triphenyl phosphorus oxygen delayed fluorescence (TADF) blue light guest materials DPXZPPO
Blue light electroluminescence phosphorescent devices voltage-brightness relation curve as shown in figure 14, thus figure understand this device the bright voltage that opens be
3.5V。
The present embodiment is with the system of thermal excitation delayed fluorescence (TADF) blue light guest materials DPXZPPO based on triphenyl phosphorus oxygen
As shown in figure 15, thus figure understands this device current effect to the luminance-current efficiency relation curve of standby blue light electroluminescence phosphorescent devices
Rate reaches maximum 15.5cd A-1。
The present embodiment is with the system of thermal excitation delayed fluorescence (TADF) blue light guest materials DPXZPPO based on triphenyl phosphorus oxygen
As shown in figure 16, thus figure understands this device power effect to the brightness of standby blue light electroluminescence phosphorescent devices-power efficiency relation curve
Rate reaches maximum 12.6lm W-1。
The present embodiment is with the system of thermal excitation delayed fluorescence (TADF) blue light guest materials DPXZPPO based on triphenyl phosphorus oxygen
As shown in figure 17, thus figure understands this device maximum to the brightness of standby blue light electroluminescence phosphorescent devices-external quantum efficiency relation curve
External quantum efficiency 10.0%.
The present embodiment is with the system of thermal excitation delayed fluorescence (TADF) blue light guest materials DPXZPPO based on triphenyl phosphorus oxygen
As shown in figure 18, thus the electroluminescent peak of this device knowable to figure exists the electroluminescent light spectrogram of standby blue light electroluminescence phosphorescent devices
At 460nm.
Embodiment nine: the present embodiment thermal excitation based on triphenyl phosphorus oxygen delayed fluorescence (TADF) blue light guest materials
The blue light electroluminescence phosphorescent devices of TPXZPPO is prepared according to the following steps:
One, the glass cleaned through deionized water or plastic being put into vacuum evaporation instrument, vacuum is 1 × 10- 6Mbar, evaporation rate is set to 0.1nm s-1, glass or plastic are deposited with tin indium oxide, thickness is that the anode of 100nm is led
Electric layer；
Two, on anode conductive layer, it is deposited with MoOx, obtains the hole injection layer that thickness is 10nm；
Three, on hole injection layer, it is deposited with NPB, obtains the hole transmission layer that thickness is 50nm；
Four, on hole transmission layer, it is deposited with mCP, obtains the electronic barrier layer that thickness is 15nm；
Five, continuing evaporation thickness on electronic barrier layer, to be that 30nm main body and thermal excitation based on triphenyl phosphorus oxygen postpone glimmering
The luminescent layer of light (TADF) blue light guest materials TPXZPPO doping, the doping content of object is 20%；
Six, on luminescent layer, it is deposited with DPEPO, obtains the hole blocking layer that thickness is 20nm；
Seven, on hole blocking layer, it is deposited with Bphen, obtains the electron transfer layer that thickness is 50nm；
Eight, it is deposited with LiF on the electron transport layer, obtains the electron injecting layer that thickness is 0.5nm；
Nine, evaporation metal Al on electron injecting layer, obtains the cathode conductive layer that thickness is 150nm, encapsulation, obtains heat shock
Send out delayed fluorescence (TADF) electroluminescent device.
The structure of the present embodiment electro phosphorescent device is: ITO/MoO3(10nm)/NPB(50nm)/mCP(15nm)/
DPEPO:TPXZPPO (20%, 30nm)/DPEPO (20nm)/Bphen (50nm)/LiF (0.5nm)/Al (150nm).
The present embodiment is prepared with thermal excitation delayed fluorescence (TADF) blue light guest materials TPXZPPO based on triphenyl phosphorus oxygen
Electro phosphorescent device voltage-current density relation curve as shown in figure 13.
The preparation of the present embodiment thermal excitation based on triphenyl phosphorus oxygen delayed fluorescence (TADF) blue light guest materials TPXZPPO
Blue light electroluminescence phosphorescent devices voltage-brightness relation curve as shown in figure 14, thus figure understand this device to open bright voltage low
In 3.5V.
The present embodiment is with the system of thermal excitation delayed fluorescence (TADF) blue light guest materials TPXZPPO based on triphenyl phosphorus oxygen
As shown in figure 15, thus figure understands this device current effect to the luminance-current efficiency relation curve of standby blue light electroluminescence phosphorescent devices
Rate reaches maximum 19.8cd A-1。
The present embodiment is with the system of thermal excitation delayed fluorescence (TADF) blue light guest materials TPXZPPO based on triphenyl phosphorus oxygen
As shown in figure 16, thus figure understands this device power effect to the brightness of standby blue light electroluminescence phosphorescent devices-power efficiency relation curve
Rate reaches maximum 17.7lm W-1。
The present embodiment is with the system of thermal excitation delayed fluorescence (TADF) blue light guest materials TPXZPPO based on triphenyl phosphorus oxygen
As shown in figure 17, thus figure understands this device maximum to the brightness of standby blue light electroluminescence phosphorescent devices-external quantum efficiency relation curve
External quantum efficiency 11.7%.
The present embodiment is with the system of thermal excitation delayed fluorescence (TADF) blue light guest materials TPXZPPO based on triphenyl phosphorus oxygen
As shown in figure 18, thus the electroluminescent peak of this device knowable to figure exists the electroluminescent light spectrogram of standby blue light electroluminescence phosphorescent devices
At 468nm.
Claims (9)
1. thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen, it is characterised in that heat based on triphenyl phosphorus oxygen
The structural formula exciting delayed fluorescence blue light guest materials is as follows:
Wherein R group isX
For
2. the preparation method of thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen described in claim 1, it is special
Levy and be that the preparation method of thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen is as follows:
1mmol phenoxazine, 1～5mmol are placed in circle to bromo-iodobenzene, 0.1～0.5mmol Hydro-Giene (Water Science)., 1～5mmol potassium carbonate
In end flask, stirring 10～36h at 120～200 DEG C, column chromatography purification obtains PXZPhBr；Take 1mmol PXZPhBr, 5～
20ml oxolane, at 0～-100 DEG C stir, drip 1～5mmol n-BuLi, reaction 10～36h after, add 1～
5mmol diphenyl phosphorus chloride stirring 5～24h, goes out reaction with shrend, adds hydrogen peroxide and stirs 1h, through petroleum ether column chromatography, acetic acid
Ethyl ester recrystallization, obtains thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen.
3. the preparation method of thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen described in claim 1, it is special
Levy and be that the preparation method of thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen is as follows:
1mmol phenoxazine, 1～5mmol are placed in circle to bromo-iodobenzene, 0.1～0.5mmol Hydro-Giene (Water Science)., 1～5mmol potassium carbonate
In end flask, stirring 10～36h at 120～200 DEG C, column chromatography purification obtains PXZPhBr or PTZPhBr；Take 2mmolPXZPhB
Or PTZPhBrr, 5～20ml oxolane, at 0～-100 DEG C stir, drip 1～15mmol n-BuLi, reaction 10～
After 36h, adding 1～5mmol or Phosphorous chloride. phenyl dichloro phosphorus stirring 5～24h, go out reaction with shrend, addition hydrogen peroxide stirs
Mix 1h, be 1:1's with ethyl acetate volume ratio with the column chromatography that petroleum ether and ethyl acetate volume ratio are 5:1 or with petroleum ether
Column chromatography, re-crystallizing in ethyl acetate, obtain thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen.
4. the preparation method of thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen described in claim 1, it is special
Levy and be that the preparation method of thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen is as follows:
1mmol phenoxazine, 1～5mmol are placed in circle to bromo-iodobenzene, 0.1～0.5mmol Hydro-Giene (Water Science)., 1～5mmol potassium carbonate
In end flask, stirring 10～36h at 120～200 DEG C, column chromatography purification obtains PXZPhBr；Take 3mmol PXZPhBr, 5～
20ml oxolane, at 0～-100 DEG C stir, drip 1～15mmol n-BuLi, reaction 10～36h after, add 1～
5mmol Phosphorous chloride. stirring 5～24h, goes out reaction with shrend, adds hydrogen peroxide stirring 1h, with petroleum ether and ethyl acetate volume
Than the column chromatography for 1:1, re-crystallizing in ethyl acetate, obtain thermal excitation delayed fluorescence blue light object material based on triphenyl phosphorus oxygen
Material.
5. the preparation method of thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen described in claim 1, it is special
Levy and be that the preparation method of thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen is as follows:
1mmol phenothiazine, 1～5mmol are placed in circle to bromo-iodobenzene, 0.1～0.5mmol Hydro-Giene (Water Science)., 1～5mmol potassium carbonate
In end flask, stirring 10～36h at 120～200 DEG C, column chromatography purification obtains PTZPhBr；Take 1mmol PTZPhBr, 5～
20ml oxolane, at 0～-100 DEG C stir, drip 1～5mmol n-BuLi, reaction 10～36h after, add 1～
5mmol diphenyl phosphorus chloride stirring 5～24h, goes out reaction with shrend, adds hydrogen peroxide and stirs 1h, through petroleum ether column chromatography, acetic acid
Ethyl ester recrystallization, obtains thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen.
6. the preparation method of thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen described in claim 1, it is special
Levy and be that the preparation method of thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen is as follows:
By 1mmol 9,9-dimethyl acridinium, 1～5mmol to bromo-iodobenzene, 0.1～0.5mmol Hydro-Giene (Water Science)., 1～5mmol carbonic acid
Potassium is placed in round-bottomed flask, stirs 10～36h at 120～200 DEG C, and column chromatography purification obtains DMACPhBr；Take 1mmol
DMACPhBr, 5～20ml oxolane, stirs at 0～-100 DEG C, drips 1～5mmol n-BuLi, reacts 10～36h
After, add 1～5mmol diphenyl phosphorus chloride stirring 5～24h, go out reaction with shrend, add hydrogen peroxide and stir 1h, through petroleum ether
Column chromatography, re-crystallizing in ethyl acetate, obtain thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen.
7. the preparation method of thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen described in claim 1, it is special
Levy and be that the preparation method of thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen is as follows:
By 1mmol 9,9-dimethyl acridinium, 1～5mmol to bromo-iodobenzene, 0.1～0.5mmol Hydro-Giene (Water Science)., 1～5mmol carbonic acid
Potassium is placed in round-bottomed flask, stirs 10～36h at 120～200 DEG C, and column chromatography purification obtains DMACPhBr；Take 2mmol
DMACPhBr, 5～20ml oxolane, stirs at 0～-100 DEG C, drips 1～10mmol n-BuLi, reacts 10～36h
After, add 1～5mmol phenyl dichloro phosphorus stirring 5～24h, go out reaction with shrend, add hydrogen peroxide and stir 1h, use petroleum ether
It is the column chromatography of 5:1 with ethyl acetate volume ratio, re-crystallizing in ethyl acetate, obtain thermal excitation based on triphenyl phosphorus oxygen and postpone glimmering
Light blue light guest materials.
8. the preparation method of thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen described in claim 1, it is special
Levy and be that the preparation method of thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen is as follows:
By 1mmol 9,9-dimethyl acridinium, 1～5mmol to bromo-iodobenzene, 0.1～0.5mmol Hydro-Giene (Water Science)., 1～5mmol carbonic acid
Potassium is placed in round-bottomed flask, stirs 10～36h at 120～200 DEG C, and column chromatography purification obtains DMACPhBr；Take 3mmol
DMACPhBr, 5～20ml oxolane, stirs at 0～-100 DEG C, drips 1～15mmol n-BuLi, reacts 10～36h
After, add 1～5mmol Phosphorous chloride. stirring 5～24h, go out reaction with shrend, add hydrogen peroxide and stir 1h, by petroleum ether and second
Acetoacetic ester volume ratio is 1:1 column chromatography, re-crystallizing in ethyl acetate, obtains thermal excitation delayed fluorescence blue light based on triphenyl phosphorus oxygen
Guest materials.
9. the application of thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen described in claim 1, its feature exists
It is applied to prepare thermal excitation delayed fluorescence in described thermal excitation delayed fluorescence blue light guest materials based on triphenyl phosphorus oxygen electroluminescent
Luminescent device.
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| CN113200929A (en) * | 2021-04-01 | 2021-08-03 | 黑龙江大学 | Cyanoquinoxaline red-light thermal excitation delayed fluorescent material, and synthesis method and application thereof |
| CN113735795A (en) * | 2021-06-25 | 2021-12-03 | 天津大学 | Organic room temperature phosphorescent material with multiple stimulus responses, and preparation method and application thereof |
| CN113735795B (en) * | 2021-06-25 | 2023-11-10 | 天津大学 | Organic room temperature phosphorescent material with multiple stimulus responses, preparation method and application |
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