CN110484241A - The dark blue photo-thermal excitation delayed fluorescence material of phosphine oxygroup boron complexes, synthetic method and its application - Google Patents
The dark blue photo-thermal excitation delayed fluorescence material of phosphine oxygroup boron complexes, synthetic method and its application Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 77
- -1 phosphine oxygroup boron complexes Chemical class 0.000 title claims abstract description 40
- 230000003111 delayed effect Effects 0.000 title claims abstract description 36
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 32
- 238000010189 synthetic method Methods 0.000 title claims abstract description 11
- 230000005284 excitation Effects 0.000 title abstract description 23
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 claims abstract description 11
- OYFFSPILVQLRQA-UHFFFAOYSA-N 3,6-ditert-butyl-9h-carbazole Chemical compound C1=C(C(C)(C)C)C=C2C3=CC(C(C)(C)C)=CC=C3NC2=C1 OYFFSPILVQLRQA-UHFFFAOYSA-N 0.000 claims abstract description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 111
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 46
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 33
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- 239000012044 organic layer Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 20
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 16
- 239000003480 eluent Substances 0.000 claims description 15
- 239000003208 petroleum Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000004090 dissolution Methods 0.000 claims description 13
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- 239000012043 crude product Substances 0.000 claims description 11
- 229910015900 BF3 Inorganic materials 0.000 claims description 10
- 239000012046 mixed solvent Substances 0.000 claims description 10
- 230000002194 synthesizing effect Effects 0.000 claims description 9
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 8
- 238000001308 synthesis method Methods 0.000 claims description 7
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 6
- 239000001632 sodium acetate Substances 0.000 claims description 6
- 235000017281 sodium acetate Nutrition 0.000 claims description 6
- XCQQWDCKLLORFE-UHFFFAOYSA-N [O].C1(=CC=CC=C1)PC1=CC=CC=C1 Chemical group [O].C1(=CC=CC=C1)PC1=CC=CC=C1 XCQQWDCKLLORFE-UHFFFAOYSA-N 0.000 claims description 5
- 150000001638 boron Chemical class 0.000 claims description 5
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- WKGDNXBDNLZSKC-UHFFFAOYSA-N oxido(phenyl)phosphanium Chemical compound O=[PH2]c1ccccc1 WKGDNXBDNLZSKC-UHFFFAOYSA-N 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 11
- ASUOLLHGALPRFK-UHFFFAOYSA-N phenylphosphonoylbenzene Chemical class C=1C=CC=CC=1P(=O)C1=CC=CC=C1 ASUOLLHGALPRFK-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000171 quenching effect Effects 0.000 abstract description 5
- HXQYLBVWDMTQFS-UHFFFAOYSA-N 1-bromo-3,6-ditert-butyl-9h-carbazole Chemical compound C1=C(C(C)(C)C)C=C2C3=CC(C(C)(C)C)=CC=C3NC2=C1Br HXQYLBVWDMTQFS-UHFFFAOYSA-N 0.000 abstract description 4
- 238000010791 quenching Methods 0.000 abstract description 2
- 239000012467 final product Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 37
- 229940125904 compound 1 Drugs 0.000 description 27
- 238000005401 electroluminescence Methods 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 12
- 229940125782 compound 2 Drugs 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 230000005525 hole transport Effects 0.000 description 6
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 238000002189 fluorescence spectrum Methods 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 3
- SCHRRICRQNJJKN-UHFFFAOYSA-N P.[O] Chemical compound P.[O] SCHRRICRQNJJKN-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 3
- 230000009878 intermolecular interaction Effects 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000003335 steric effect Effects 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 229910000085 borane Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- OKZIUSOJQLYFSE-UHFFFAOYSA-N difluoroboron Chemical class F[B]F OKZIUSOJQLYFSE-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- NTUCWBPMVKOIDS-UHFFFAOYSA-N 1,8-dibromo-3,6-ditert-butyl-9h-carbazole Chemical compound C1=C(C(C)(C)C)C=C2C3=CC(C(C)(C)C)=CC(Br)=C3NC2=C1Br NTUCWBPMVKOIDS-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- REAYFGLASQTHKB-UHFFFAOYSA-N [2-[3-(1H-pyrazol-4-yl)phenoxy]-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound N1N=CC(=C1)C=1C=C(OC2=NC(=CC(=C2)CN)C(F)(F)F)C=CC=1 REAYFGLASQTHKB-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012795 verification 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
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/572—Five-membered rings
- C07F9/5728—Five-membered rings condensed with carbocyclic rings or carbocyclic ring systems
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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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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- 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
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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
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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Abstract
Phosphine oxygroup boron complexes dark blue photo-thermal excitation delayed fluorescence material, synthetic method and its application, it is related to a kind of thermal excitation delayed fluorescence material, synthetic method and its application.The present invention be in order to solve the problems, such as existing dark blue smooth TADF material due to divide concentration quenching and electroluminescent device efficiency it is relatively low and decaying it is fast.This material structure formula is as follows:Synthetic method: the bromo- 3,6- di-t-butyl -9H- carbazole of preparation 1- or the bromo- 3,6- di-t-butyl -9H- carbazole of 1,8- bis-；(3,6- di-t-butyl -9H- carbazole -1- base) diphenyl phosphine oxide or (3,6- di-t-butyl -9H- carbazole -1,8- diyl) bis- (diphenyl phosphine oxides) are prepared, final product is obtained.Material of the present invention is obviously improved the efficiency of electroluminescent device, reduces quenching effect, enhances the stabilised efficiency of electroluminescent device.The invention belongs to the preparation fields of fluorescent material.
Description
Technical field
The present invention relates to a kind of thermal excitation delayed fluorescence material, synthetic method and its applications.
Background technique
Organic electroluminescence device (organic light-emitting diodes, OLEDs) has low energy consumption, color
Abundant, quick response and the features such as flexible device can be prepared, it is considered to be most promising next-generation FPD
With solid state lighting technology.Currently, the research to OLED has been achieved for remarkable break-throughs.1st generation based on fluorescent emissive materials
For OLED because shining with only singlet excitons, internal quantum efficiency (IQE) only has 25%.2nd generation OLED is based on noble metal
Phosphorescent emissive material, singlet state (25%) is fully utilized by the Quantum geometrical phase (SOC) between noble metal and its ligand
With triplet (75%) exciton, IQE is up to 100%.However, phosphorescent emissive material has the following problems: 1. heavy metal prices are high
It is high；2. efficiency can decline phosphorescent OLED under high currents；3. efficient and stable blue phosphorescent OLED is not easy to be made.In order to avoid
Using heavy metal, people begin trying new solution.Hot activation delayed fluorescence (TADF) material is brought
New solution, since the energy level difference between its lowest excited singlet state and lowest excited triplet is smaller, triplet swashs
Son can be transformed into singlet state by altering between inverse system in more process, it is glimmering to realize that the triplet exciton of non precious metal addition participates in
Light emitting substantially increases luminous efficiency, and theoretical internal quantum efficiency is enable to reach 100%.Because TADF material is fundamentally
Internal quantum efficiency is improved, and avoids the use of heavy metal, so TADF becomes third generation electroluminescent organic material.
In recent years simultaneously, aromatic phosphines oxygen class material causes the great interest of people due to the advantage that its own is protruded, quilt
For the efficient electroluminescent material of main part of design construction and luminescent material etc..Phosphine oxygen (P=O) group will by C-P saturated bond
Aromatic group connects, and can be effectively blocked the extension of conjugation, guarantees that the launch wavelength of material is not affected；P=O simultaneously
Group has the function of polar molecule, and the electron injection transmittability of material can be improved；In addition, diphenylphosphine oxygen groups also have
Biggish space steric effect, can be effectively suppressed intermolecular interaction.Therefore, phosphine oxygroup is introduced in donor-receiver structure
Group can be under the premise of not influencing material launch wavelength, and molecular configuration and electric property to material etc. are adjusted, thus
To efficient blue TADF material
Summary of the invention
The purpose of the present invention is to solve existing blue-light-emitting guest materials because being easy to appear T-T annihilation
And the problem of concentration quenching under high doping, and provide a kind of dark blue photo-thermal excitation delayed fluorescence material of phosphine oxygroup boron complexes, synthesis
Method and its application.
The dark blue photo-thermal excitation delayed fluorescence material structure formula of phosphine oxygroup boron complexes is as follows:
When X is diphenylphosphine oxygroup, and Y is H, structural formula are as follows:
When X is diphenylphosphine oxygroup, and Y is diphenylphosphine oxygroup, structural formula are as follows:
The dark blue photo-thermal of phosphine oxygroup boron complexes excites delayed fluorescence material synthesis method, it is characterised in that the synthesis side
Method is as follows:
One, the dissolution of 3, the 6- di-t-butyl carbazole of 3~5mmol is placed in reaction flask in methylene chloride, by 5~
In the N- bromo-succinimide dissolution dimethylformamide of 10mmol, pours into constant pressure funnel and be added dropwise at normal temperature, normal
It is stirred to react under temperature to completion of dropwise addition, is extracted with water and methylene chloride, merge organic layer, remove organic solvent after dry, obtain slightly
Product obtains bromo- 3, the 6- di-t-butyl -9- methyl -9H- carbazole of 1- or 1,8- bis- using petroleum ether as eluent column chromatographic purifying
Bromo- 3,6- di-t-butyl -9H- carbazole.
Two, the product for synthesizing 3~5mml step 1, the palladium acetate of 0.025~0.05mmol, the acetic acid of 5~10mmol
After sodium is placed under the conditions of anhydrous and oxygen-free, diphenylphosphine and 50ml under the conditions of keeping anhydrous and oxygen-free by it with 6~12mmol
Dimethylformamide mixing, is stirred to react 12 hours at 140 DEG C, is cooled to room temperature after reaction, is extracted with water and methylene chloride
It takes, merges organic layer, extract, merge organic by organic layer and 10ml hydroperoxidation 2 hours, then with water and methylene chloride
Layer removes organic solvent after dry, obtains crude product, chromatographs using the mixed solvent of petroleum ether and ethyl acetate as eluent column pure
Change, obtains (3,6- di-t-butyl -9H- carbazole -1- base) diphenyl phosphine oxide or (3,6- di-t-butyl -9H- carbazoles -1,8- bis-
Base) bis- (diphenyl phosphine oxides).
Three, the product for synthesizing 1.0~1.5mmol step 2,4.6mmol triethylamine and 4~7.9mmol boron trifluoride second
Ether dissolution reacts 50 DEG C for 24 hours in methylene chloride, is extracted with water and methylene chloride, merges organic layer, removes after dry organic molten
Agent obtains crude product, using the mixed solvent of petroleum ether and ethyl acetate as eluent column chromatographic purifying, obtains (3,6- di-t-butyls-
9- (difluoroboryl) -9H- carbazole -1- base) diphenyl phosphine oxide boron complexes or (3,6- di-t-butyl -9- (difluoro borine
Base) -9H- carbazole -1,8- diyl) bis- (diphenyl phosphine oxide) boron complexes.
The dark blue photo-thermal excitation delayed fluorescence material of phosphine oxygroup boron complexes is used for organic electroluminescence as emitting layer material
Luminescent device.
The dark blue photo-thermal excitation delayed fluorescence material application of phosphine oxygroup boron complexes is as follows:
Conductive layer is first made, hole transport layer material is then deposited on the electrically conductive, phosphine oxygen is deposited on the hole transport layer
The doping body luminescent layer of base boron complexes dark blue photo-thermal excitation delayed fluorescence material and material of main part, is deposited electronics on the light-emitting layer
Layer material is transmitted, second layer conductive layer is finally deposited.
The doping body is CBP and the dark blue photo-thermal excitation delayed fluorescence of phosphine oxygroup boron complexes is material doped.
The dark blue photo-thermal excitation delayed fluorescence material of phosphine oxygroup boron complexes provided by the invention is will be electric by aromatic group
Sub- 3,6 di-t-butyl carbazole of donor, electron acceptor boron trifluoride and Co receptor diphenylphosphine oxygen groups, three kinds of functional groups have
It connects together to effect, to construct the electroluminescent material of aromatic phosphines oxygen blue based on boron trifluoride.Wherein, electron donor is mainly 3,
6 di-t-butyl carbazoles, the hole transport performance of material can be enhanced in it；Electron acceptor mainly includes having strong electrophilic fluorination
Boron group, to adjust the launch wavelength of material to blue region；Co receptor is mainly diphenylphosphine oxygroup group, weak by its
Sucting electronic effect finely tune the photoelectric properties of material, in addition its big steric effect can be enhanced material thermal stability and at
Film properties simultaneously effectively inhibit quenching effect caused by intermolecular interaction.
The dark blue photo-thermal excitation delayed fluorescence material of phosphine oxygroup boron complexes of the present invention is used for electroluminescent as luminescent material
Device includes following advantages:
1, thermal excitation delayed fluorescence material can utilize singlet and Triplet exciton simultaneously, be obviously improved electroluminescent
The efficiency of device；
2, intermolecular interaction can be effectively suppressed in the biggish space steric effect of material molecule, reduces quenching effect, increases
The stabilised efficiency of forceful electric power electroluminescence device.
3, the electron injection and transmittability of material can be improved in the polarization of phosphine oxygen groups, reduces electroluminescent device
Driving voltage.
Detailed description of the invention
Fig. 1 is the Ultraluminescence spectrum spectrogram for testing the compound 1 of a synthesis, and wherein ■ is indicated in dichloromethane solvent
Ultraviolet spectrogram, ● indicate that the ultraviolet spectrogram of film, indicate the fluorescence spectra in dichloromethane solvent, zero indicates film
Fluorescence spectra；
Fig. 2 is the thermogravimetric analysis spectrogram for testing the compound 1 of a synthesis；
Fig. 3 is the Ultraluminescence spectrum spectrogram for testing the compound 2 of two synthesis, and wherein ■ is indicated in dichloromethane solvent
Ultraviolet spectrogram, ● indicate that the ultraviolet spectrogram of film, indicate the fluorescence spectra in dichloromethane solvent, zero indicates film
Fluorescence spectra, △ indicate 77K under the conditions of fluorescence spectra；
Fig. 4 is the thermogravimetric analysis spectrogram for testing the compound 2 of two synthesis；
Fig. 5 is the voltage-current density relation curve of the doping type red electroluminescent TADF device prepared with compound 1；
Fig. 6 is the voltage-brightness relation curve of the doping type red electroluminescent TADF device prepared with compound 1；
Fig. 7 is that current density-current efficiency relationship of the doping type red electroluminescent TADF device prepared with compound 1 is bent
Line；
Fig. 8 is that current density-power efficiency relationship of the doping type red electroluminescent TADF device prepared with compound 1 is bent
Line；
Fig. 9 is that current density-external quantum efficiency relationship of the doping type red electroluminescent TADF device prepared with compound 1 is bent
Line；
Figure 10 is the electroluminescent light spectrogram of the doping type red electroluminescent TADF device prepared with compound 1；
Specific embodiment
The technical solution of the present invention is not limited to the following list, further includes between each specific embodiment
Any combination.
Specific embodiment 1: the dark blue photo-thermal of present embodiment phosphine oxygroup boron complexes excites delayed fluorescence material structure formula
It is as follows:
When X is diphenylphosphine oxygroup, and Y is H, structural formula are as follows:
When X is diphenylphosphine oxygroup, and Y is diphenylphosphine oxygroup, structural formula are as follows:
Specific embodiment 2: the dark blue photo-thermal of phosphine oxygroup boron complexes described in specific embodiment one excites delayed fluorescence material
Expect that synthetic method, the synthetic method are as follows:
The dissolution of 3, the 6- di-t-butyl carbazole of 3~5mmol is placed in reaction flask by one, in methylene chloride, by 5~
In the N- bromo-succinimide dissolution dimethylformamide of 10mmol, pours into constant pressure funnel and be added dropwise at normal temperature, normal
It is stirred to react under temperature to completion of dropwise addition, is extracted with water and methylene chloride, merge organic layer, remove organic solvent after dry, obtain slightly
Product obtains bromo- 3, the 6- di-t-butyl -9- methyl -9H- carbazole of 1- or 1,8- bis- using petroleum ether as eluent column chromatographic purifying
Bromo- 3,6- di-t-butyl -9H- carbazole.
The product that two, synthesize 3~5mml step 1, the palladium acetate of 0.025~0.05mmol, the acetic acid of 5~10mmol
After sodium is placed under the conditions of anhydrous and oxygen-free, diphenylphosphine and 50ml under the conditions of keeping anhydrous and oxygen-free by it with 6~12mmol
Dimethylformamide mixing, is stirred to react 12 hours at 140 DEG C, is cooled to room temperature after reaction, is extracted with water and methylene chloride
It takes, merges organic layer, extract, merge organic by organic layer and 10ml hydroperoxidation 2 hours, then with water and methylene chloride
Layer removes organic solvent after dry, obtains crude product, chromatographs using the mixed solvent of petroleum ether and ethyl acetate as eluent column pure
Change, obtains (3,6- di-t-butyl -9H- carbazole -1- base) diphenyl phosphine oxide or (3,6- di-t-butyl -9H- carbazoles -1,8- bis-
Base) bis- (diphenyl phosphine oxides).
The product that three, synthesize 1.0~1.5mmol step 2,4.6mmol triethylamine and 4~7.9mmol boron trifluoride second
Ether dissolution reacts 50 DEG C for 24 hours in methylene chloride, is extracted with water and methylene chloride, merges organic layer, removes after dry organic molten
Agent obtains crude product, using the mixed solvent of petroleum ether and ethyl acetate as eluent column chromatographic purifying, obtains (3,6- di-t-butyls-
9- (difluoroboryl) -9H- carbazole -1- base) diphenyl phosphine oxide boron complexes or (3,6- di-t-butyl -9- (difluoro borine
Base) -9H- carbazole -1,8- diyl) bis- (diphenyl phosphine oxide) boron complexes.
Specific embodiment 3: present embodiment from unlike specific embodiment two in step 1 by the 3 of 5mmol,
The dissolution of 6- di-t-butyl carbazole is placed in reaction flask in methylene chloride, and the N- bromo-succinimide of 50mmol is dissolved diformazan
In base formamide.Other are identical with embodiment two.
Specific embodiment 4: present embodiment 5mmol in step 1 unlike specific embodiment two or three
The dissolution of 3,6- di-t-butyl carbazoles is placed in reaction flask in methylene chloride, and the N- bromo-succinimide of 10mmol is dissolved two
In methylformamide,
Specific embodiment 5: present embodiment uses in step 1 unlike specific embodiment two to four
The N- bromo-succinimide of 5mmol uses 0.025mmol palladium acetate, 5mmol sodium acetate, 6mmol diphenyl in step 2
Phosphorus, step 3 use 4mmol boron trifluoride ether, obtain compound 1, other are identical as specific embodiment two to four.
Specific embodiment 6: present embodiment uses in step 1 unlike specific embodiment two to five
The N- bromo-succinimide of 10mmol uses 0.05mmol palladium acetate, 10mmol sodium acetate, 12mmol diphenyl in step 2
Phosphorus, step 3 use 7.9mmol boron trifluoride ether, obtain compound 2, other are identical as specific embodiment two to five.
Specific embodiment 7: the dark blue photo-thermal of phosphine oxygroup boron complexes described in specific embodiment one excites delayed fluorescence material
Material is used for organic electroluminescence device as emitting layer material.
Specific embodiment 8: present embodiment phosphine oxygroup boron complexes unlike specific embodiment seven are deep
The application of blue light thermal excitation delayed fluorescence material is as follows:
Conductive layer is first made, hole transport layer material is then deposited on the electrically conductive, phosphine oxygen is deposited on the hole transport layer
The doping body luminescent layer of base red orange photo-thermal excitation delayed fluorescence material and material of main part, is deposited electron transfer layer on the light-emitting layer
Second layer conductive layer is finally deposited in material.Other are identical as specific embodiment seven.
Specific embodiment 9: present embodiment doping body unlike specific embodiment seven or eight is CBP
It is material doped with the red orange photo-thermal excitation delayed fluorescence of phosphine oxygroup.Other are identical as specific embodiment seven or eight.
Specific embodiment 10: the application method is such as unlike specific embodiment seven or eight for present embodiment
Under:
One, tin indium oxide (ITO) is deposited on glass or plastic supporting base and is used as anode conductive layer, with a thickness of 1~100nm；
Two, evaporation material NPB is as hole transmission layer on anode conductive layer, with a thickness of 2~10nm；
Three, on the hole transport layer the mixture of evaporation material CBP and compound 1-6 as luminescent layer, with a thickness of 20~
40nm；
Four, evaporation material TPBi is as electron transfer layer on the light-emitting layer, with a thickness of 5~50nm；
Five, evaporation metal (Al) is used as cathode conductive layer on the electron transport layer, and with a thickness of 1~100nm, encapsulation obtains electricity
Electroluminescence device.
Specific embodiment 11: luminescent layer material described in step 3 unlike present embodiment specific embodiment ten
Material be CBP respectively with compound 1, compound 2, formed mixture, wherein compound 1, compound 2 mass concentration be 5%.
Using following experimental verifications effect of the present invention:
Experiment one: the synthetic method of the dark blue photo-thermal excitation delayed fluorescence material compound 1 of this experiment phosphine oxygroup boron complexes
It follows these steps to realize:
One, 3, the 6- di-t-butyl carbazole dissolution of 5mmol is placed in reaction flask in methylene chloride, by the N- of 5mmol
Bromo-succinimide dissolves in dimethylformamide, pours into constant pressure funnel and is added dropwise at normal temperature, and stirring is anti-at normal temperature
It should be extracted to completion of dropwise addition with water and methylene chloride, merge organic layer, remove organic solvent after dry, crude product is obtained, with petroleum
Ether is eluent column chromatographic purifying, obtains bromo- 3, the 6- di-t-butyl -9- methyl -9H- carbazole of 1-.
Two, the sodium acetate of the product for synthesizing 5mml step 1, the palladium acetate of 0.025mmol, 5mmol is placed in anhydrous and oxygen-free
Under the conditions of after, it is mixed with the diphenylphosphine of 6mmol with the dimethylformamide of 50ml under the conditions of keeping anhydrous and oxygen-free, In
140 DEG C are stirred to react 12 hours, are cooled to room temperature after reaction, are extracted with water and methylene chloride, merge organic layer, will be organic
Layer with 10ml hydroperoxidation 2 hours, then extracted with water and methylene chloride, merge organic layer, remove organic solvent after drying,
It obtains crude product and obtains (3,6- di-t-butyl -9H- using the mixed solvent of petroleum ether and ethyl acetate as eluent column chromatographic purifying
Carbazole -1- base) diphenyl phosphine oxide.
Three, the product for synthesizing 1.5mmol step 2,4.6mmol triethylamine and 4mmol boron trifluoride ether are dissolved in two
50 DEG C are reacted in chloromethanes for 24 hours, is extracted with water and methylene chloride, are merged organic layer, are removed organic solvent after dry, obtain and slightly produce
Product obtain (3,6- di-t-butyl -9- (boron difluorides using the mixed solvent of petroleum ether and ethyl acetate as eluent column chromatographic purifying
Alkyl) -9H- carbazole -1- base) diphenyl phosphine oxide boron complexes.That is compound 1
Bromo- 3, the 6- di-t-butyl -9- methyl -9H- carbazole of 1- prepared by this experimental procedure one, structural formula are as follows:
(3,6- di-t-butyl -9H- carbazole -1- base) diphenyl phosphine oxide of step 2 preparation, structural formula are as follows:
According to its flight time matter of the bromo- 3,6- di-t-butyl -9- methyl -9H- carbazole of 1- of step 1 preparation in experiment one
The data of spectrum are as follows: m/z (%): 357 (100) [M+]；The data of elemental analysis are as follows: molecular formula C20H24BrN theoretical value: C 63.94,
H 4.03, N 3.58, measured value: C 67.04, H 6.75, N3.91.
(3,6- di-t-butyl -9H- carbazole -1- base) diphenyl phosphine oxide of step 2 preparation, flight time mass spectrum
Data are as follows: m/z (%): 479 (100) [M+]；The data of elemental analysis are as follows: molecular formula C32H34NOP theoretical value: C 80.13, H
7.13, N2.92, measured value: C 80.14, H 7.15, N2.92.
The compound 1 of step 3 preparation, the data of flight time mass spectrum are as follows: m/z (%): 527 (100) [M+]；Element
The data of analysis are as follows: molecular formula C32H33BF2NOP, theoretical value: C 72.88, H 6.33, N 2.64；Measured value: C 72.88, H
6.31,N 2.66.This experiment obtains the Ultraluminescence of the dark blue photo-thermal excitation delayed fluorescence material compound 1 of phosphine oxygroup boron complexes
Spectrum spectrogram is as shown in Figure 1.
This experiment obtains the thermogravimetric analysis spectrogram of the dark blue photo-thermal excitation delayed fluorescence material compound 1 of phosphine oxygroup boron complexes
As shown in Fig. 2, the cracking temperature of compound 1 is up to 302 DEG C as seen from the figure.
Experiment two: the synthetic method of the dark blue photo-thermal excitation delayed fluorescence material compound 2 of this experiment phosphine oxygroup boron complexes
It follows these steps to realize:
One, 3, the 6- di-t-butyl carbazole dissolution of 5mmol is placed in reaction flask in methylene chloride, by the N- of 10mmol
Bromo-succinimide dissolves in dimethylformamide, pours into constant pressure funnel and is added dropwise at normal temperature, and stirring is anti-at normal temperature
It should be extracted to completion of dropwise addition with water and methylene chloride, merge organic layer, remove organic solvent after dry, crude product is obtained, with petroleum
Ether is eluent column chromatographic purifying, obtains bromo- 3, the 6- di-t-butyl -9H- carbazole of 1,8- bis-.
Two, the sodium acetate of the product for synthesizing 5mml step 1, the palladium acetate of 0.05mmol, 10mmol is placed in anhydrous and oxygen-free
Under the conditions of after, it is mixed with the diphenylphosphine of 12mmol with the dimethylformamide of 50ml under the conditions of keeping anhydrous and oxygen-free,
It is stirred to react at 140 DEG C 12 hours, is cooled to room temperature after reaction, extracted with water and methylene chloride, merge organic layer, will have
Machine layer with 10ml hydroperoxidation 2 hours, then extracted with water and methylene chloride, merge organic layer, removed after drying organic molten
Agent obtains crude product, using the mixed solvent of petroleum ether and ethyl acetate as eluent column chromatographic purifying, obtains (3,6- di-t-butyls-
9H- carbazole -1,8- diyl) bis- (diphenyl phosphine oxides).
Three, the product for synthesizing 1.5mmol step 2,4.6mmol triethylamine and 7.9mmol boron trifluoride ether are dissolved in
50 DEG C are reacted in methylene chloride for 24 hours, is extracted with water and methylene chloride, are merged organic layer, are removed organic solvent after dry, obtain and slightly produce
Product obtain (3,6- di-t-butyl -9- (boron difluorides using the mixed solvent of petroleum ether and ethyl acetate as eluent column chromatographic purifying
Alkyl) -9H- carbazole -1,8- diyl) bis- (diphenyl phosphine oxide) boron complexes.That is compound 2.
Bromo- 3, the 6- di-t-butyl -9H- carbazole of 1,8- bis- prepared by this experimental procedure one, structural formula are as follows:
(3,6- di-t-butyl -9H- carbazole -1,8- diyl) bis- (diphenyl phosphine oxides) of step 2 preparation, structural formula
Are as follows:
According to 1,8- bis- bromo- 3,6- di-t-butyl -9H- carbazole its flight time mass spectrum of step 1 preparation in experiment one
Data are as follows: m/z (%): 437 (100) [M+]；The data of elemental analysis are as follows: molecular formula C20H23Br2N theoretical value: C 54.90, H
5.33, N3.20, measured value: C 54.93, H 5.30, N3.20.
(3,6- di-t-butyl -9H- carbazole -1,8- diyl) bis- (diphenyl phosphine oxides) of step 2 preparation, when flight
Between mass spectrographic data are as follows: m/z (%): 679 (100) [M+]；The data of elemental analysis are as follows: molecular formula C44H43NO2P2Theoretical value: C
77.72, H 6.40, N2.06, measured value: 77.74, H 6.38, N2.06.
The compound 2 of step 3 preparation, the data of flight time mass spectrum are as follows: m/z (%): 689 (100) [M+]；Element
The data of analysis are as follows: molecular formula C44H42BF2NO2P2, theoretical value: C, 76.66；H,6.12；N,2.03；Measured value: C, 72.64；
H,5.82；N,1.93.
This experiment obtains the Ultraluminescence spectrum of the dark blue photo-thermal excitation delayed fluorescence material compound 2 of phosphine oxygroup boron complexes
Spectrogram is as shown in Figure 3.
This experiment obtains the thermogravimetric analysis spectrogram of the dark blue photo-thermal excitation delayed fluorescence material compound 2 of phosphine oxygroup boron complexes
As shown in figure 4, the cracking temperature of compound 1 is up to 433.8 DEG C as seen from the figure.
Application Example one: the present embodiment excites delayed fluorescence material compound 1 with the dark blue photo-thermal of phosphine oxygroup boron complexes
Blue light electroluminescence TADF device for emitting layer material preparation is prepared according to the following steps:
Luminescent layer be compound 1 and 4, the doping body of 4 '-two (9- carbazole) biphenyl (CBP), evaporation film-forming, with a thickness of
40nm.Hole transmission layer (N, N '-two that upper a layer thickness is 10nm are deposited between anode (tin indium oxide ITO) and luminescent layer
Phenyl-N, N '-(1- naphthalene) -1,1 '-biphenyl -4,4 '-diamines, NPB).Electron transfer layer material therefor is (the 1- benzene of 1,3,5- tri-
Base -1H- benzimidazolyl-2 radicals-yl) benzene (TPBi), film thickness 10nm.Electrode material is aluminium, with a thickness of 100nm.The knot of device
Structure is ITO/NPB (10nm)/CBP:1 (40nm)/TPBi (10nm)/Al (100nm)
The voltage-current density relation curve such as Figure 13 for the blue light electroluminescence TADF device that the present embodiment is prepared with compound 1
Shown, thus compound 1 known to figure has characteristic of semiconductor, threshold voltage 4V.
The present embodiment is as shown in figure 14 with the voltage-brightness relation curve of blue light electroluminescence TADF device prepared by compound 1,
Thus the maximum brightness of the device known to figure is up to 954.7cdm-2。
Current density-current efficiency the relation curve for the blue light electroluminescence TADF device that the present embodiment is prepared with compound 1 is such as
Shown in Figure 15, thus the device known to figure is 0.50mAcm in current density-2When, current efficiency reaches maximum value 8.09cd
A-1。
Current density-the power efficiency relation curve for the blue light electroluminescence TADF device that the present embodiment is prepared with compound 1 is such as
Shown in Figure 16, thus the device known to figure is 0.50mAcm in current density-2When, power efficiency reaches maximum value 5.08lm
W-1。
Current density-external quantum efficiency the relation curve for the blue light electroluminescence TADF device that the present embodiment is prepared with compound 1
As shown in figure 17, the device is 0.08mAcm in current density known to thus scheming-2When, obtain maximum external quantum efficiency
6.82%.
The present embodiment is as shown in figure 18 with the electroluminescent light spectrogram of blue light electroluminescence TADF device prepared by compound 1, by
The electroluminescent peak of the device is at 440nm known to this figure.
Claims (6)
1. the dark blue photo-thermal of phosphine oxygroup boron complexes excites delayed fluorescence material, it is characterised in that the phosphine oxygroup boron complexes are dark blue
Photo-thermal excites delayed fluorescence material structure formula as follows:；
When X is diphenylphosphine oxygen, and Y is diphenylphosphine oxygen, structural formula are as follows:
When X is diphenylphosphine oxygen, and Y is H, structural formula are as follows:
。
2. the dark blue photo-thermal of phosphine oxygroup boron complexes described in claim 1 excites delayed fluorescence material synthesis method, it is characterised in that
The synthetic method is as follows:
One, 3, the 6- di-t-butyl carbazole dissolution of 3~5mmol is placed in reaction flask in methylene chloride, by 5~10mmol's
N- bromo-succinimide dissolves in dimethylformamide, pours into constant pressure funnel and is added dropwise at normal temperature, stirs at normal temperature
Reaction is extracted with water and methylene chloride to completion of dropwise addition, merges organic layer, remove organic solvent after dry, crude product is obtained, with stone
Oily ether is eluent column chromatographic purifying, obtains bromo- 3, the 6- di-t-butyl -9- methyl -9H- carbazole of 1- or 1, bromo- 3, the 6- bis- of 8- bis-
Tert-butyl -9H- carbazole.；
Two, the product for synthesizing 3~5mml step 1, the sodium acetate of the palladium acetate of 0.025~0.05mmol, 5~10mmol are set
After under the conditions of anhydrous and oxygen-free, by itself and the diphenylphosphine of 6~12mmol and the diformazan of 50ml under the conditions of keeping anhydrous and oxygen-free
The mixing of base formamide, is stirred to react 12 hours at 140 DEG C, is cooled to room temperature after reaction, is extracted with water and methylene chloride, closes
And organic layer, it is extracted by organic layer and 10ml hydroperoxidation 2 hours, then with water and methylene chloride, merges organic layer, it is dry
After remove organic solvent, obtain crude product, using the mixed solvent of petroleum ether and ethyl acetate as eluent column chromatographic purifying, obtain
(3,6- di-t-butyl -9H- carbazole -1- base) diphenyl phosphine oxide or (3,6- di-t-butyl -9H- carbazole -1,8- diyl) bis- (two
Phenyl phosphine oxide).
Three, the product for synthesizing 1.0~1.5mmol step 2,4.6mmol triethylamine and 4~7.9mmol boron trifluoride ether are molten
Solution reacts 50 DEG C for 24 hours in methylene chloride, is extracted with water and methylene chloride, merges organic layer, removes organic solvent after dry, obtain
Crude product obtains (3,6- di-t-butyl -9- (two using the mixed solvent of petroleum ether and ethyl acetate as eluent column chromatographic purifying
Fluorine boryl) -9H- carbazole -1- base) diphenyl phosphine oxide boron complexes or (3,6- di-t-butyl -9- (difluoroboryl) -9H-
Carbazole -1,8- diyl) bis- (diphenyl phosphine oxide) boron complexes.
3. exciting delayed fluorescence material synthesis method according to the dark blue photo-thermal of phosphine oxygroup boron complexes described in right 2, it is characterised in that
By in the N- bromo-succinimide dissolution dimethylformamide of 5mmol or 10mmol in step 1, constant pressure funnel is poured into
It is added dropwise at normal temperature.
4. exciting delayed fluorescence material synthesis method according to the dark blue photo-thermal of phosphine oxygroup boron complexes described in right 2, it is characterised in that
The palladium acetate of the product that 5mml step 1 will be synthesized in step 2,0.025mmol or 0.05mmol, 5mmol or 10mmol's
After sodium acetate is placed under the conditions of anhydrous and oxygen-free, by the diphenylphosphine of itself and 6mmol or 12mmol under the conditions of keeping anhydrous and oxygen-free
It is mixed with the dimethylformamide of 50ml.
5. exciting delayed fluorescence material synthesis method according to the dark blue photo-thermal of phosphine oxygroup boron complexes described in right 2, it is characterised in that
By organic layer and 10ml hydroperoxidation 2 hours in step 2, then extracted with water and methylene chloride.
6. exciting delayed fluorescence material synthesis method according to the dark blue photo-thermal of phosphine oxygroup boron complexes described in right 2, it is characterised in that
The product for synthesizing 1.5mmol step 2 in step 3,4.6mmol triethylamine and 3.5mmol or 7.9mmol boron trifluoride ether
Dissolution reacts 50 DEG C for 24 hours in methylene chloride.
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