CN110128460A - A kind of siliceous electroluminescent organic material and preparation method thereof - Google Patents
A kind of siliceous electroluminescent organic material and preparation method thereof Download PDFInfo
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- CN110128460A CN110128460A CN201910440669.5A CN201910440669A CN110128460A CN 110128460 A CN110128460 A CN 110128460A CN 201910440669 A CN201910440669 A CN 201910440669A CN 110128460 A CN110128460 A CN 110128460A
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- siliceous
- organic material
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- phenyl
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- 239000011368 organic material Substances 0.000 title claims abstract description 133
- 238000002360 preparation method Methods 0.000 title claims abstract description 95
- UDZSLJULKCKKPX-UHFFFAOYSA-N (4-bromophenyl)-triphenylsilane Chemical compound C1=CC(Br)=CC=C1[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 UDZSLJULKCKKPX-UHFFFAOYSA-N 0.000 claims abstract description 61
- 150000001502 aryl halides Chemical class 0.000 claims abstract description 59
- 125000003118 aryl group Chemical group 0.000 claims abstract description 56
- 239000004327 boric acid Substances 0.000 claims abstract description 50
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 50
- 150000002367 halogens Chemical class 0.000 claims abstract description 50
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 48
- OIRHKGBNGGSCGS-UHFFFAOYSA-N 1-bromo-2-iodobenzene Chemical compound BrC1=CC=CC=C1I OIRHKGBNGGSCGS-UHFFFAOYSA-N 0.000 claims abstract description 34
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims abstract description 20
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 171
- 238000006243 chemical reaction Methods 0.000 claims description 59
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 56
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 52
- 239000000243 solution Substances 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- 238000003756 stirring Methods 0.000 claims description 43
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 34
- 230000015572 biosynthetic process Effects 0.000 claims description 32
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 32
- 238000003786 synthesis reaction Methods 0.000 claims description 31
- 229910052757 nitrogen Inorganic materials 0.000 claims description 28
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims description 24
- ZGNPLWZYVAFUNZ-UHFFFAOYSA-N tert-butylphosphane Chemical compound CC(C)(C)P ZGNPLWZYVAFUNZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000010189 synthetic method Methods 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 22
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 21
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 20
- 239000012044 organic layer Substances 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 18
- 229910002027 silica gel Inorganic materials 0.000 claims description 18
- 239000000741 silica gel Substances 0.000 claims description 18
- 229960001866 silicon dioxide Drugs 0.000 claims description 18
- 238000010792 warming Methods 0.000 claims description 18
- 238000010992 reflux Methods 0.000 claims description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 235000019441 ethanol Nutrition 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 14
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 12
- 229910000077 silane Inorganic materials 0.000 claims description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 10
- 238000006467 substitution reaction Methods 0.000 claims description 9
- -1 2- aminofluorene compound Chemical class 0.000 claims description 8
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 6
- PKJBWOWQJHHAHG-UHFFFAOYSA-N 1-bromo-4-phenylbenzene Chemical group C1=CC(Br)=CC=C1C1=CC=CC=C1 PKJBWOWQJHHAHG-UHFFFAOYSA-N 0.000 claims description 5
- ZOQCZTRFTARYGJ-UHFFFAOYSA-N chlorooxy(phenyl)borinic acid Chemical compound ClOB(O)C1=CC=CC=C1 ZOQCZTRFTARYGJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims 2
- 235000011181 potassium carbonates Nutrition 0.000 claims 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- DLIJPAHLBJIQHE-UHFFFAOYSA-N butylphosphane Chemical compound CCCCP DLIJPAHLBJIQHE-UHFFFAOYSA-N 0.000 claims 1
- GTPDFCLBTFKHNH-UHFFFAOYSA-N chloro(phenyl)silicon Chemical compound Cl[Si]C1=CC=CC=C1 GTPDFCLBTFKHNH-UHFFFAOYSA-N 0.000 claims 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims 1
- 229940072033 potash Drugs 0.000 claims 1
- 235000015320 potassium carbonate Nutrition 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 20
- 238000005401 electroluminescence Methods 0.000 abstract description 7
- 230000005540 biological transmission Effects 0.000 abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052710 silicon Inorganic materials 0.000 abstract description 4
- 239000010703 silicon Substances 0.000 abstract description 4
- 230000005525 hole transport Effects 0.000 abstract description 2
- 125000005259 triarylamine group Chemical group 0.000 abstract description 2
- AKQNYQDSIDKVJZ-UHFFFAOYSA-N triphenylsilane Chemical compound C1=CC=CC=C1[SiH](C=1C=CC=CC=1)C1=CC=CC=C1 AKQNYQDSIDKVJZ-UHFFFAOYSA-N 0.000 description 13
- 230000007423 decrease Effects 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- XRPOYNNXPVJDNQ-UHFFFAOYSA-N (2-bromophenyl)-triphenylsilane Chemical compound BrC1=CC=CC=C1[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 XRPOYNNXPVJDNQ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- CYSPWCARDHRYJX-UHFFFAOYSA-N 9h-fluoren-1-amine Chemical compound C12=CC=CC=C2CC2=C1C=CC=C2N CYSPWCARDHRYJX-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- BFRDBSBKJUVSNP-UHFFFAOYSA-N 9h-fluorene;silicon Chemical class [Si].C1=CC=C2CC3=CC=CC=C3C2=C1 BFRDBSBKJUVSNP-UHFFFAOYSA-N 0.000 description 2
- PMLRYPYQSAIBPM-UHFFFAOYSA-N C1=CC=CC=C1.[I].[Br] Chemical compound C1=CC=CC=C1.[I].[Br] PMLRYPYQSAIBPM-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 150000002220 fluorenes Chemical class 0.000 description 2
- 230000001002 morphogenetic effect Effects 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000000007 visual effect Effects 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/0827—Syntheses with formation of a Si-C bond
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/083—Syntheses without formation of a Si-C bond
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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
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- H—ELECTRICITY
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- H10K50/00—Organic light-emitting devices
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- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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Abstract
A kind of siliceous electroluminescent organic material and preparation method thereof, it belongs to electroluminescent organic material Material Field.This synthesizes 4- bromophenyl tri-phenyl-silane with to bromo-iodobenzene by tri-phenyl chloride first, then the synthetic product of the halogen aryl boric acid replaced by 4- bromophenyl tri-phenyl-silane and contraposition, aryl halides and 9, the synthetic product of 9- alkyl -2- aminofluorene compound is respectively synthesized a kind of siliceous electroluminescent organic material that a kind of siliceous electroluminescent organic material and R1 that R1 is unsubstituted is substituted base.The siliceous electroluminescent organic material of one kind of the present invention, containing the fluorene structured triarylamine compounds of class, has preferable hole transport performance, can be used as the hole transmission layer in organic electroluminescence device centered on silicon tetraphenyl.A kind of siliceous electroluminescent organic material of the invention has preferable thermal stability.
Description
Technical field
The invention belongs to electroluminescent organic material Material Fields；More particularly to a kind of siliceous electroluminescent organic material
And preparation method thereof.
Background technique
In recent years, Organic Light Emitting Diode (Organic Light-Emitting Diode, OLED) due to its is small in size,
It is light-weight, driving voltage is low, response is fast, visual angle is wide and can realize large area full color flat panel display the advantages that become it is non-at home and abroad
Often popular New flat panel display industry.
Usually using multilayered structure in OLED device, these multilayered structures include luminescent layer and various auxiliary organic layers,
Wherein, the hole transmission layer effect in luminescent layer is the cavity transmission ability of enhancing device, while by electronic blocking in luminescent layer
It is interior, to improve the recombination probability in electronics and hole.The film forming of hole mobile material and its thermal stability of film are for mentioning
The efficiency of high organic electroluminescence device and service life play an important role.
Being used as the most of of organic hole transport material at present is aromatic triamine class compound, because of aromatic triamine class
Compound has low ionization energy, and the N atom on tertiary amine has very strong electron donation, and formation cation easy to oxidize is certainly
Electropositivity is shown by base (hole).In various electroluminescent organic materials, fluorenes class has rigid structure and higher light
Thermal stability, in solid-state, the absolute photoluminescence quantum efficiencies of fluorenes are up to 60-80%, and band-gap energy is greater than 2.90eV, because forming
It common are machine luminescent material and auxiliary material for one kind, but brightness, luminous efficiency, driving stability and service life etc. still need to
It is further to improve.
And the film that siliceous cavitation material is formed on the electrode can effectively improve the flatness of electrode surface, form nothing
The film of pin hole, but also need to further increase the glass transition temperature of siliceous cavitation material.
Summary of the invention
The object of the present invention is to provide a kind of siliceous electroluminescent organic materials and preparation method thereof.
The present invention is achieved through the following technical solutions:
A kind of siliceous electroluminescent organic material, the general structure of the siliceous electroluminescent organic material of described one kind
Are as follows:
Wherein, R1 group are as follows: unsubstituted or aryl or xenyl；R2 group are as follows: aryl or xenyl or naphthalene；R3 base
Group structural formula be
The preparation method of the siliceous electroluminescent organic material of one kind of the present invention, includes the following steps:
Step a, it the synthesis of 4- bromophenyl tri-phenyl-silane: is prepared by tri-phenyl chloride with to bromo-iodobenzene, for use；
Step b, the synthesis for the halogen aryl boric acid that 4- bromophenyl tri-phenyl-silane and contraposition replace: 4- bromophenyl triphen is obtained
The synthetic product for the halogen aryl boric acid that base silane and contraposition replace；
Step c, the synthesis of aryl halides and 9,9- alkyl -2- aminofluorene compound, obtains aryl halides and 9,9-
The synthetic product of alkyl -2- aminofluorene compound；
Step d, R1 is a kind of synthesis of siliceous electroluminescent organic material of unsubstituted；
Step e, R1 is a kind of synthesis of siliceous electroluminescent organic material of substituted base.
The preparation method of the siliceous electroluminescent organic material of one kind of the present invention, 4- bromophenyl triphen in step a
The synthetic method of base silane, includes the following steps:
It step a1, is that 1:1:1 is weighed to bromo-iodobenzene, butyl lithium, tri-phenyl chloride, for use respectively according to molar ratio；
Step a2, under the protection of nitrogen, tetrahydrofuran is added under stirring conditions to bromo-iodobenzene by step a1 is weighed
Solvent, the mass ratio to bromo-iodobenzene and the tetrahydrofuran are 1:6, then, are cooled to -80~-75 DEG C, step is added dropwise
The weighed butyl lithium of rapid a1, reacts 1~2 hour at -80~-75 DEG C after dropwise addition, obtains reaction solution, for use；
Step a3, tetrahydrofuran solvent is added in the weighed tri-phenyl chloride of step a1 under stirring conditions, it is described
Tri-phenyl chloride and the mass ratio of the tetrahydrofuran be 1:3, obtained mixed solution is under the protection of nitrogen, stirring
Under the conditions of be slowly dropped to the reaction solution that step a2 is obtained, then heat to 0 DEG C, into reaction system be added to 2 times of bromo-iodobenzene
The pure water of quality hydrolyzes 0.5~1h, is concentrated under reduced pressure, obtains product a, for use；
Step a4, the anhydrous methanol to 2 times of quality of bromo-iodobenzene is added in product a made from step a3, stirs 30min, mistake
Filter, after drying, obtains 4- bromophenyl tri-phenyl-silane.
The preparation method of the siliceous electroluminescent organic material of one kind of the present invention, 4- bromophenyl triphen in step a
The equation of the synthesis of base silane is as follows:
The preparation method of the siliceous electroluminescent organic material of one kind of the present invention, bromo-iodobenzene is replaced in step a1
It is changed to paradibromobenzene.
The preparation method of the siliceous electroluminescent organic material of one kind of the present invention, 4- bromophenyl tri-phenyl-silane
Yield is 85%, purity 99.5%.
The preparation method of the siliceous electroluminescent organic material of one kind of the present invention, 4- bromophenyl triphen in step b
The synthetic method for the halogen aryl boric acid that base silane and contraposition replace, includes the following steps:
It step b1, is that 1:1.1:2.5:0.001 weighs 4- bromophenyl tri-phenyl-silane respectively, contraposition replaces according to molar ratio
Halogen aryl boric acid, potassium carbonate, tetra-triphenylphosphine palladium, for use；
Step b2, the weighed 4- bromophenyl tri-phenyl-silane of step b1 is dissolved in toluene, obtains 4- in alcohol mixed solvent
The mass ratio of bromophenyl tri-phenyl-silane mixed solution, the 4- bromophenyl tri-phenyl-silane and toluene, ethyl alcohol is 1:10:
1.5, the weighed potassium carbonate of step b1 is dissolved in pure water, the concentration of dissolved wet chemical is 2.5mol/L, will
Wet chemical is added in the 4- bromophenyl tri-phenyl-silane mixed solution, adds the weighed contraposition of step b1 and replaces
Halogen aryl boric acid, under the protection of nitrogen, stirring be warming up to 70 DEG C of micro- reflux, after being then cooled to 65 DEG C be added step b1 claim
The tetra-triphenylphosphine palladium taken obtains reaction solution b, for use in 72~73 DEG C of 4~5h of back flow reaction；
Step b3, the pure water of 1 times of volume is added in the reaction solution b for obtaining step b2, and organic layer is 60~70 after dividing water
Silicagel column is crossed under the conditions of DEG C, after efflux steams the toluene of 3/4 times of volume, is rapidly added 3 times of ethyl alcohol, is cooled down under stirring condition
To 15 DEG C, filtering after drying, obtains the synthetic product of the halogen aryl boric acid of 4- bromophenyl tri-phenyl-silane and contraposition substitution.
The preparation method of the siliceous electroluminescent organic material of one kind of the present invention, 4- bromophenyl triphen in step b
The equation of the synthesis for the halogen aryl boric acid that base silane replaces with contraposition is as follows:
The preparation method of the siliceous electroluminescent organic material of one kind of the present invention aligns substituted halogen in step b1
Aryl boric acid is to chlorophenylboronic acid.
The preparation method of the siliceous electroluminescent organic material of one kind of the present invention, the 4- bromophenyl triphenyl
The yield of the synthetic product for the halogen aryl boric acid that silane and contraposition replace is 88.3%, purity 99.5%, HPLC Detection wavelength
For 254nm.
The preparation method of the siliceous electroluminescent organic material of one kind of the present invention, in step c aryl halides with
The synthetic method of 9,9- alkyl -2- aminofluorene compounds, includes the following steps:
It step c1, is that 1:0.95:0.001:0.004:1.5 weighs aryl halides, 9,9- alkyl-respectively according to molar ratio
2- aminofluorene compound, Pd2(DBA)3, tert-butyl phosphine, sodium tert-butoxide, for use；
Step c2, the weighed aryl halides of step c1 are dissolved in toluene solvant, the aryl halides with it is described
Toluene mass ratio be 1:10, then add load weighted 9, the 9- alkyl -2- aminofluorene compound of step c1, Pd2
(DBA)3, tert-butyl phosphine, sodium tert-butoxide be warming up to reflux under nitrogen protection, react 2~4h, obtain reaction solution c, for use；
Step c3, the pure water of 1 times of volume is added in the reaction solution c for obtaining step c2, and organic layer is 60~70 after dividing water
Silicagel column is crossed under the conditions of DEG C, after efflux steams the toluene of 3/5 times of volume, is rapidly added 3 times of isopropanol, stirring condition decline
For temperature to 15 DEG C, filtering after drying, obtains the synthetic product of aryl halides Yu 9,9- alkyl -2- aminofluorene compound.
The preparation method of the siliceous electroluminescent organic material of one kind of the present invention, in step c aryl halides with
The synthesis equation of 9,9- alkyl -2- aminofluorene compound is as follows:
The preparation method of the siliceous electroluminescent organic material of one kind of the present invention, aryl halides are in step c1
4- bromo biphenyl, 9,9- alkyl -2- aminofluorene compounds are 9,9- dimethyl -2- amino substance.
The preparation method of the siliceous electroluminescent organic material of one kind of the present invention, aryl halides and 9,9- alkane
The yield of the synthetic product of base -2- aminofluorene compound is 92%, purity 99.5%.
The preparation method of the siliceous electroluminescent organic material of one kind of the present invention, R1 is unsubstituted in step d
The siliceous electroluminescent organic material of described one kind synthetic method, include the following steps:
Step d1, the 4- bromophenyl of step a preparation is weighed respectively for 1:0.95:0.001:0.004:1.5 according to molar ratio
Synthetic product, the Pd of tri-phenyl-silane, the aryl halides of step c preparation and 9,9- alkyl -2- aminofluorene compound2(DBA)3、
Tert-butyl phosphine, sodium tert-butoxide, for use；
Step d2, the weighed 4- bromophenyl tri-phenyl-silane of step d1 is dissolved in toluene solvant, the 4- bromophenyl
The mass ratio of tri-phenyl-silane and the toluene is 1:10, then adds the load weighted aryl halides of step d1 and 9,9-
Synthetic product, the Pd of alkyl -2- aminofluorene compound2(DBA)3, tert-butyl phosphine, sodium tert-butoxide be warming up under nitrogen protection
Reflux reacts 2~4h, obtains reaction solution d, for use；
Step d3, the pure water of 1 times of volume is added in the reaction solution d for obtaining step d2, and organic layer is 60~70 after dividing water
Silicagel column is crossed under the conditions of DEG C, after efflux steams the toluene of 3/5 times of volume, is rapidly added 3 times of isopropanol, stirring condition decline
Temperature is to 15 DEG C, filtering, after drying, obtains the siliceous electroluminescent organic material of described one kind of unsubstituted.
The preparation method of the siliceous electroluminescent organic material of one kind of the present invention, R1 is unsubstituted in step d
The siliceous electroluminescent organic material of described one kind synthesis equation it is as follows:
The preparation method of the siliceous electroluminescent organic material of one kind of the present invention, it is unsubstituted for synthesizing the R1
The yield of the siliceous electroluminescent organic material of described one kind of base is 85.7%, purity 99.6%, HPLC Detection wavelength
For 254nm, UV absorption wavelength is 345nm.
The preparation method of the siliceous electroluminescent organic material of one kind of the present invention, R1 is substituted base in step e
The siliceous electroluminescent organic material of described one kind synthetic method, include the following steps:
Step e1, the 4- bromophenyl of step b preparation is weighed respectively for 1:0.95:0.001:0.004:1.5 according to molar ratio
Aryl halides and 9,9- alkyl -2- prepared by synthetic product, the step c for the halogen aryl boric acid that tri-phenyl-silane and contraposition replace
Synthetic product, the Pd of aminofluorene compound2(DBA)3, tert-butyl phosphine, sodium tert-butoxide, for use；
Step e2, the synthesis for the halogen aryl boric acid that the weighed 4- bromophenyl tri-phenyl-silane of step e1 and contraposition replace is produced
Object is dissolved in toluene solvant, the synthetic product of the halogen aryl boric acid of the 4- bromophenyl tri-phenyl-silane and contraposition substitution and institute
The mass ratio for the toluene stated is 1:10, then adds the load weighted aryl halides of step e1 and 9,9- alkyl -2- aminofluorene
Synthetic product, the Pd of compound2(DBA)3, tert-butyl phosphine, sodium tert-butoxide be warming up to reflux under nitrogen protection, reaction 2~
4h obtains reaction solution e, for use；
Step e3, the pure water of 1 times of volume is added in the reaction solution e for obtaining step e2, and organic layer is 60~70 after dividing water
Silicagel column is crossed under the conditions of DEG C, after efflux steams the toluene of 3/5 times of volume, is rapidly added 3 times of isopropanol, stirring condition decline
Temperature is to 15 DEG C, filtering, after drying, obtains the siliceous electroluminescent organic material of described one kind of substituted base.
The preparation method of the siliceous electroluminescent organic material of one kind of the present invention, R1 is substituted base in step e
The siliceous electroluminescent organic material of described one kind synthesis equation it is as follows:
The preparation method of the siliceous electroluminescent organic material of one kind of the present invention, it is substituted for synthesizing the R1
The yield of the siliceous electroluminescent organic material of described one kind of base is 88.6%, purity 99.7%, HPLC Detection wavelength
For 254nm, UV absorption wavelength is 361nm.
Described one kind of the preparation method preparation of the siliceous electroluminescent organic material of one kind of the present invention is siliceous
Electroluminescent organic material synthesized novel silicon-fluorenes class hole mobile material in conjunction with the advantages of silicon, fluorene material, have compared with
Good thermal stability.
Described one kind of the preparation method preparation of the siliceous electroluminescent organic material of one kind of the present invention is siliceous
Electroluminescent organic material containing the fluorene structured triarylamine compounds of class, there is preferable hole centered on silicon tetraphenyl
Transmission performance can be used as the hole transmission layer in organic electroluminescence device.
Detailed description of the invention
Fig. 1 is the nuclear-magnetism spectrum of the siliceous electroluminescent organic material of described one kind of one method of specific embodiment preparation
Figure；
Fig. 2 is the nuclear-magnetism spectrum of the siliceous electroluminescent organic material of described one kind of one method of specific embodiment preparation
The partial enlarged view of figure；
Fig. 3 is the thermogravimetric spectrum of the siliceous electroluminescent organic material of described one kind of one method of specific embodiment preparation
Figure；
Fig. 4 is the ultraviolet suction of the siliceous electroluminescent organic material of described one kind of one method of specific embodiment preparation
Receive spectrogram；
Fig. 5 is the ultraviolet suction of the siliceous electroluminescent organic material of described one kind of two method of specific embodiment preparation
Receive spectrogram.
Specific embodiment
Specific embodiment 1:
A kind of preparation method for the electroluminescent organic material that one kind described in claim 1 is siliceous, includes the following steps:
Step a, it the synthesis of 4- bromophenyl tri-phenyl-silane: is prepared by tri-phenyl chloride with to bromo-iodobenzene, for use；
Step b, the synthesis for the halogen aryl boric acid that 4- bromophenyl tri-phenyl-silane and contraposition replace: 4- bromophenyl triphen is obtained
The synthetic product for the halogen aryl boric acid that base silane and contraposition replace；
Step c, the synthesis of aryl halides and 9,9- alkyl -2- aminofluorene compound, obtains aryl halides and 9,9-
The synthetic product of alkyl -2- aminofluorene compound；
Step d, R1 is a kind of synthesis of siliceous electroluminescent organic material of substituted base.
The preparation method of the siliceous electroluminescent organic material of one kind described in present embodiment, 4- bromophenyl in step a
The synthetic method of tri-phenyl-silane, includes the following steps:
It step a1, is that 1:1:1 is weighed to bromo-iodobenzene, butyl lithium, tri-phenyl chloride, for use respectively according to molar ratio；
Step a2, under the protection of nitrogen, tetrahydrofuran is added under stirring conditions to bromo-iodobenzene by step a1 is weighed
Solvent, the mass ratio to bromo-iodobenzene and the tetrahydrofuran are 1:6, then, are cooled to -80~-75 DEG C, step is added dropwise
The weighed butyl lithium of rapid a1, reacts 1~2 hour at -80~-75 DEG C after dropwise addition, obtains reaction solution, for use；
Step a3, tetrahydrofuran solvent is added in the weighed tri-phenyl chloride of step a1 under stirring conditions, it is described
Tri-phenyl chloride and the mass ratio of the tetrahydrofuran be 1:3, obtained mixed solution is under the protection of nitrogen, stirring
Under the conditions of be slowly dropped to the reaction solution that step a2 is obtained, then heat to 0 DEG C, into reaction system be added to 2 times of bromo-iodobenzene
The pure water of quality hydrolyzes 0.5~1h, is concentrated under reduced pressure, obtains product a, for use；
Step a4, the anhydrous methanol to 2 times of quality of bromo-iodobenzene is added in product a made from step a3, stirs 30min, mistake
Filter, after drying, obtains 4- bromophenyl tri-phenyl-silane.
The preparation method of the siliceous electroluminescent organic material of one kind described in present embodiment, in step a1 to bromine iodine
Benzene replaces with paradibromobenzene.
The preparation method of the siliceous electroluminescent organic material of one kind described in present embodiment, 4- bromophenyl in step b
The synthetic method for the halogen aryl boric acid that tri-phenyl-silane and contraposition replace, includes the following steps:
It step b1, is that 1:1.1:2.5:0.001 weighs 4- bromophenyl tri-phenyl-silane respectively, contraposition replaces according to molar ratio
Halogen aryl boric acid, potassium carbonate, tetra-triphenylphosphine palladium, for use；
Step b2, the weighed 4- bromophenyl tri-phenyl-silane of step b1 is dissolved in toluene, obtains 4- in alcohol mixed solvent
The mass ratio of bromophenyl tri-phenyl-silane mixed solution, the 4- bromophenyl tri-phenyl-silane and toluene, ethyl alcohol is 1:10:
1.5, the weighed potassium carbonate of step b1 is dissolved in pure water, the concentration of dissolved wet chemical is 2.5mol/L, will
Wet chemical is added in the 4- bromophenyl tri-phenyl-silane mixed solution, adds the weighed contraposition of step b1 and replaces
Halogen aryl boric acid, under the protection of nitrogen, stirring be warming up to 70 DEG C of micro- reflux, after being then cooled to 65 DEG C be added step b1 claim
The tetra-triphenylphosphine palladium taken obtains reaction solution b, for use in 72~73 DEG C of 4~5h of back flow reaction；
Step b3, the pure water of 1 times of volume is added in the reaction solution b for obtaining step b2, and organic layer is 60~70 after dividing water
Silicagel column is crossed under the conditions of DEG C, after efflux steams the toluene of 3/4 times of volume, is rapidly added 3 times of ethyl alcohol, is cooled down under stirring condition
To 15 DEG C, filtering after drying, obtains the synthetic product of the halogen aryl boric acid of 4- bromophenyl tri-phenyl-silane and contraposition substitution.
The preparation method of the siliceous electroluminescent organic material of one kind described in present embodiment aligns in step b1 and replaces
Halogen aryl boric acid be to chlorophenylboronic acid.
The preparation method of the siliceous electroluminescent organic material of one kind described in present embodiment, aryl halide generation in step c
Object and 9, the synthetic method of 9- alkyl -2- aminofluorene compound, includes the following steps:
It step c1, is that 1:0.95:0.001:0.004:1.5 weighs aryl halides, 9,9- alkyl-respectively according to molar ratio
2- aminofluorene compound, Pd2(DBA)3, tert-butyl phosphine, sodium tert-butoxide, for use；
Step c2, the weighed aryl halides of step c1 are dissolved in toluene solvant, the aryl halides with it is described
Toluene mass ratio be 1:10, then add load weighted 9, the 9- alkyl -2- aminofluorene compound of step c1, Pd2
(DBA)3, tert-butyl phosphine, sodium tert-butoxide be warming up to reflux under nitrogen protection, react 2~4h, obtain reaction solution c, for use；
Step c3, the pure water of 1 times of volume is added in the reaction solution c for obtaining step c2, and organic layer is 60~70 after dividing water
Silicagel column is crossed under the conditions of DEG C, after efflux steams the toluene of 3/5 times of volume, is rapidly added 3 times of isopropanol, stirring condition decline
For temperature to 15 DEG C, filtering after drying, obtains the synthetic product of aryl halides Yu 9,9- alkyl -2- aminofluorene compound.
The preparation method of the siliceous electroluminescent organic material of one kind described in present embodiment, aryl halide generation in step c1
Object is 4- bromo biphenyl, and 9,9- alkyl -2- aminofluorene compounds are 9,9- dimethyl -2- amino substance.
The preparation method of the siliceous electroluminescent organic material of one kind described in present embodiment, R1 is to take in step d
The synthetic method of the siliceous electroluminescent organic material of described one kind of Dai Ji, includes the following steps:
Step d1, the 4- bromophenyl of step b preparation is weighed respectively for 1:0.95:0.001:0.004:1.5 according to molar ratio
Aryl halides and 9,9- alkyl -2- prepared by synthetic product, the step c for the halogen aryl boric acid that tri-phenyl-silane and contraposition replace
Synthetic product, the Pd of aminofluorene compound2(DBA)3, tert-butyl phosphine, sodium tert-butoxide, for use；
Step d2, the synthesis for the halogen aryl boric acid that the weighed 4- bromophenyl tri-phenyl-silane of step d1 and contraposition replace is produced
Object is dissolved in toluene solvant, the synthetic product of the halogen aryl boric acid of the 4- bromophenyl tri-phenyl-silane and contraposition substitution and institute
The mass ratio for the toluene stated is 1:10, then adds the load weighted aryl halides of step e1 and 9,9- alkyl -2- aminofluorene
Synthetic product, the Pd of compound2(DBA)3, tert-butyl phosphine, sodium tert-butoxide be warming up to reflux under nitrogen protection, reaction 2~
4h obtains reaction solution e, for use；
Step d3, the pure water of 1 times of volume is added in the reaction solution e for obtaining step d2, and organic layer is 60~70 after dividing water
Silicagel column is crossed under the conditions of DEG C, after efflux steams the toluene of 3/5 times of volume, is rapidly added 3 times of isopropanol, stirring condition decline
Temperature is to 15 DEG C, filtering, after drying, obtains the siliceous electroluminescent organic material of described one kind of substituted base.
Described one kind of the preparation method preparation of the siliceous electroluminescent organic material of one kind described in present embodiment
Siliceous electroluminescent organic material, carries out nuclear magnetic resonance test, and NMR spectrum can subtly symbolize each proton
Distribution of charges situation, the property of complex and the relationship of structure, nuclear magnetic spectrogram institute as shown in Figure 1, Figure 2 are illustrated from microcosmic level
Show, from Fig. 1, Fig. 2, it can be seen that,1H NMR(400MHz,Chloroform-d)δ7.66–7.59(m,14H),7.53(t,J
=8.6Hz, 4H), 7.46-7.36 (m, 12H), 7.33-7.27 (m, 4H), 7.25-7.22 (m, 4H), 7.12 (d, J=8.3Hz,
1H), 1.44 (s, 6H), it was demonstrated that the preparation method system of the siliceous electroluminescent organic material of one kind described in this present embodiment
The structural formula of the siliceous electroluminescent organic material of the standby described one kind is as follows:
Described one kind of the preparation method preparation of the siliceous electroluminescent organic material of one kind described in present embodiment
Siliceous electroluminescent organic material, thermogravimetric spectrogram is as shown in figure 3, it can be seen that described one kind of preparation is siliceous from Fig. 3
Electroluminescent organic material decomposition temperature be 436 DEG C, illustrate the compound have preferable heat resistanceheat resistant capacity of decomposition, also illustrate
Target compound has preferable thermal stability.
Described one kind of the preparation method preparation of the siliceous electroluminescent organic material of one kind described in present embodiment
Siliceous electroluminescent organic material, the UV absorption spectrogram measured in toluene solvant as shown in figure 4, from Fig. 4, it can be seen that
In toluene solution, the siliceous electroluminescent organic material of described one kind has a strong absworption peak in 360nm or so, this be by
In π-π * transition and the morphogenetic absorption peak of Intramolecular electron transfer.The light of the siliceous electroluminescent organic material of described one kind
Learning band gap can be by formula: Eg opt=1241/ λmaxIt estimates, wherein Eg optRepresent the siliceous organic electroluminescence material of described one kind
The optical band gap of material, unit eV, λmaxFor the wave on the absorption maximum side of the siliceous electroluminescent organic material of described one kind
It is long, unit nm, numerical value 361nm, therefore can be calculated the light of the siliceous electroluminescent organic material of described one kind
Band gap is 3.44eV.
Described one kind of the preparation method preparation of the siliceous electroluminescent organic material of one kind described in present embodiment
Siliceous electroluminescent organic material synthesizes a kind of siliceous organic electroluminescence material that the R1 is substituted base
The yield of material is 88.6%, purity 99.7%.
Described one kind of the preparation method preparation of the siliceous electroluminescent organic material of one kind described in present embodiment
Siliceous electroluminescent organic material has synthesized novel silicon-fluorenes class hole mobile material in conjunction with the advantages of silicon, fluorene material, tool
There are preferable electron, lower ionization potential, higher hole mobility, preferable dissolubility and amorphous film-forming
Property, stronger fluorescence property and photostability, while also having many advantages, such as that low energy consumption, luminous efficiency is high and long service life.
Specific embodiment 2:
A kind of preparation method for the electroluminescent organic material that one kind described in claim 1 is siliceous, it is characterised in that: packet
Include following steps:
Step a, it the synthesis of 4- bromophenyl tri-phenyl-silane: is prepared by tri-phenyl chloride with to bromo-iodobenzene, for use；
Step b, the synthesis for the halogen aryl boric acid that 4- bromophenyl tri-phenyl-silane and contraposition replace: 4- bromophenyl triphen is obtained
The synthetic product for the halogen aryl boric acid that base silane and contraposition replace；
Step c, the synthesis of aryl halides and 9,9- alkyl -2- aminofluorene compound, obtains aryl halides and 9,9-
The synthetic product of alkyl -2- aminofluorene compound；
Step d, R1 is a kind of synthesis of siliceous electroluminescent organic material of unsubstituted.
The preparation method of the siliceous electroluminescent organic material of one kind described in present embodiment, 4- bromophenyl in step a
The synthetic method of tri-phenyl-silane, includes the following steps:
It step a1, is that 1:1:1 is weighed to bromo-iodobenzene, butyl lithium, tri-phenyl chloride, for use respectively according to molar ratio；
Step a2, under the protection of nitrogen, tetrahydrofuran is added under stirring conditions to bromo-iodobenzene by step a1 is weighed
Solvent, the mass ratio to bromo-iodobenzene and the tetrahydrofuran are 1:6, then, are cooled to -80~-75 DEG C, step is added dropwise
The weighed butyl lithium of rapid a1, reacts 1~2 hour at -80~-75 DEG C after dropwise addition, obtains reaction solution, for use；
Step a3, tetrahydrofuran solvent is added in the weighed tri-phenyl chloride of step a1 under stirring conditions, it is described
Tri-phenyl chloride and the mass ratio of the tetrahydrofuran be 1:3, obtained mixed solution is under the protection of nitrogen, stirring
Under the conditions of be slowly dropped to the reaction solution that step a2 is obtained, then heat to 0 DEG C, into reaction system be added to 2 times of bromo-iodobenzene
The pure water of quality hydrolyzes 0.5~1h, is concentrated under reduced pressure, obtains product a, for use；
Step a4, the anhydrous methanol to 2 times of quality of bromo-iodobenzene is added in product a made from step a3, stirs 30min, mistake
Filter, after drying, obtains 4- bromophenyl tri-phenyl-silane.
The preparation method of the siliceous electroluminescent organic material of one kind described in present embodiment, in step a1 to bromine iodine
Benzene replaces with paradibromobenzene.
The preparation method of the siliceous electroluminescent organic material of one kind described in present embodiment, 4- bromophenyl in step b
The synthetic method for the halogen aryl boric acid that tri-phenyl-silane and contraposition replace, includes the following steps:
It step b1, is that 1:1.1:2.5:0.001 weighs 4- bromophenyl tri-phenyl-silane respectively, contraposition replaces according to molar ratio
Halogen aryl boric acid, potassium carbonate, four-triphenylphosphines-palladium, for use；
Step b2, the weighed 4- bromophenyl tri-phenyl-silane of step b1 is dissolved in toluene, obtains 4- in alcohol mixed solvent
The mass ratio of bromophenyl tri-phenyl-silane mixed solution, the 4- bromophenyl tri-phenyl-silane and toluene, ethyl alcohol is 1:10:
1.5, the weighed potassium carbonate of step b1 is dissolved in pure water, the concentration of dissolved wet chemical is 2.5mol/L, will
Wet chemical is added in the 4- bromophenyl tri-phenyl-silane mixed solution, adds the weighed contraposition of step b1 and replaces
Halogen aryl boric acid, under the protection of nitrogen, stirring be warming up to 70 DEG C of micro- reflux, after being then cooled to 65 DEG C be added step b1 claim
Four-triphenylphosphines-the palladium taken obtains reaction solution b, for use in 72~73 DEG C of 4~5h of back flow reaction；
Step b3, the pure water of 1 times of volume is added in the reaction solution b for obtaining step b2, and organic layer is 60~70 after dividing water
Silicagel column is crossed under the conditions of DEG C, after efflux steams the toluene of 3/4 times of volume, is rapidly added 3 times of ethyl alcohol, is cooled down under stirring condition
To 15 DEG C, filtering after drying, obtains the synthetic product of the halogen aryl boric acid of 4- bromophenyl tri-phenyl-silane and contraposition substitution.
The preparation method of the siliceous electroluminescent organic material of one kind described in present embodiment aligns in step b1 and replaces
Halogen aryl boric acid be to chlorophenylboronic acid.
The preparation method of the siliceous electroluminescent organic material of one kind described in present embodiment, aryl halide generation in step c
Object and 9, the synthetic method of 9- alkyl -2- aminofluorene compound, includes the following steps:
It step c1, is that 1:0.95:0.001:0.004:1.5 weighs aryl halides, 9,9- alkyl-respectively according to molar ratio
2- aminofluorene compound, Pd2(DBA)3, tert-butyl phosphine, sodium tert-butoxide, for use；
Step c2, the weighed aryl halides of step c1 are dissolved in toluene solvant, the aryl halides with it is described
Toluene mass ratio be 1:10, then add load weighted 9, the 9- alkyl -2- aminofluorene compound of step c1, Pd2
(DBA)3, tert-butyl phosphine, sodium tert-butoxide be warming up to reflux under nitrogen protection, react 2~4h, obtain reaction solution c, for use；
Step c3, the pure water of 1 times of volume is added in the reaction solution c for obtaining step c2, and organic layer is 60~70 after dividing water
Silicagel column is crossed under the conditions of DEG C, after efflux steams the toluene of 3/5 times of volume, is rapidly added 3 times of isopropanol, stirring condition decline
For temperature to 15 DEG C, filtering after drying, obtains the synthetic product of aryl halides Yu 9,9- alkyl -2- aminofluorene compound.
The preparation method of the siliceous electroluminescent organic material of one kind described in present embodiment, aryl halide generation in step c1
Object is 4- bromo biphenyl, and 9,9- alkyl -2- aminofluorene compounds are 9,9- dimethyl -2- amino substance.
The preparation method of the siliceous electroluminescent organic material of one kind described in present embodiment, R1 is without taking in step d
The synthetic method of the siliceous electroluminescent organic material of described one kind of Dai Ji, includes the following steps:
Step d1, the 4- bromophenyl of step a preparation is weighed respectively for 1:0.95:0.001:0.004:1.5 according to molar ratio
Synthetic product, the Pd of tri-phenyl-silane, the aryl halides of step c preparation and 9,9- alkyl -2- aminofluorene compound2(DBA)3、
Tert-butyl phosphine, sodium tert-butoxide, for use；
Step d2, the weighed 4- bromophenyl tri-phenyl-silane of step d1 is dissolved in toluene solvant, the 4- bromophenyl
The mass ratio of tri-phenyl-silane and the toluene is 1:10, then adds the load weighted aryl halides of step d1 and 9,9-
Synthetic product, the Pd of alkyl -2- aminofluorene compound2(DBA)3, tert-butyl phosphine, sodium tert-butoxide be warming up under nitrogen protection
Reflux reacts 2~4h, obtains reaction solution d, for use；
Step d3, the pure water of 1 times of volume is added in the reaction solution d for obtaining step d2, and organic layer is 60~70 after dividing water
Silicagel column is crossed under the conditions of DEG C, after efflux steams the toluene of 3/5 times of volume, is rapidly added 3 times of isopropanol, stirring condition decline
Temperature is to 15 DEG C, filtering, after drying, obtains the siliceous electroluminescent organic material of described one kind of unsubstituted.
Described one kind of the preparation method preparation of the siliceous electroluminescent organic material of one kind described in present embodiment
Siliceous electroluminescent organic material, the UV absorption spectrogram measured in toluene solvant as shown in figure 5, from Fig. 5, it can be seen that
In toluene solution, the siliceous electroluminescent organic material of described one kind has a strong absworption peak in 345nm or so, this be by
In π-π * transition and the morphogenetic absorption peak of Intramolecular electron transfer.The light of the siliceous electroluminescent organic material of described one kind
Learning band gap can be by formula: Eg opt=1241/ λmaxIt estimates, wherein Eg optRepresent the siliceous organic electroluminescence material of described one kind
The optical band gap of material, unit eV, λmaxFor the wave on the absorption maximum side of the siliceous electroluminescent organic material of described one kind
It is long, unit nm, numerical value 345nm, therefore can be calculated the light of the siliceous electroluminescent organic material of described one kind
Band gap is 3.60eV.
Described one kind of the preparation method preparation of the siliceous electroluminescent organic material of one kind described in present embodiment
Siliceous electroluminescent organic material synthesizes a kind of siliceous organic electroluminescence material that the R1 is unsubstituted
The yield of material is 85.7%, purity 99.6%.
Specific embodiment 3:
A kind of siliceous electroluminescent organic material, the general structure of the siliceous electroluminescent organic material of described one kind
Are as follows:
Wherein, R1 group are as follows: unsubstituted or aryl or xenyl；R2 group are as follows: aryl or xenyl or naphthalene or pyrene
Base or anthryl；The structural formula of R3 group is
Specific embodiment 4:
According to the preparation method of the siliceous electroluminescent organic material of one kind described in specific embodiment one, including it is as follows
Step:
Step a, it the synthesis of 4- bromophenyl tri-phenyl-silane: is prepared by tri-phenyl chloride with to bromo-iodobenzene, for use；
Step b, the synthesis for the halogen aryl boric acid that 4- bromophenyl tri-phenyl-silane and contraposition replace: 4- bromophenyl triphen is obtained
The synthetic product for the halogen aryl boric acid that base silane and contraposition replace；
Step c, the synthesis of aryl halides and 9,9- alkyl -2- aminofluorene compound, obtains aryl halides and 9,9-
The synthetic product of alkyl -2- aminofluorene compound；
Step d, R1 is a kind of synthesis of siliceous electroluminescent organic material of unsubstituted；
Step e, R1 is a kind of synthesis of siliceous electroluminescent organic material of substituted base.
Specific embodiment 5:
According to the preparation method of the siliceous electroluminescent organic material of one kind described in specific embodiment four, in step a
The synthetic method of 4- bromophenyl tri-phenyl-silane, includes the following steps:
It step a1, is that 1:1:1 is weighed to bromo-iodobenzene, butyl lithium, tri-phenyl chloride, for use respectively according to molar ratio；
Step a2, under the protection of nitrogen, tetrahydrofuran is added under stirring conditions to bromo-iodobenzene by step a1 is weighed
Solvent, the mass ratio to bromo-iodobenzene and the tetrahydrofuran are 1:6, then, are cooled to -80~-75 DEG C, step is added dropwise
The weighed butyl lithium of rapid a1, reacts 1~2 hour at -80~-75 DEG C after dropwise addition, obtains reaction solution, for use；
Step a3, tetrahydrofuran solvent is added in the weighed tri-phenyl chloride of step a1 under stirring conditions, it is described
Tri-phenyl chloride and the mass ratio of the tetrahydrofuran be 1:3, obtained mixed solution is under the protection of nitrogen, stirring
Under the conditions of be slowly dropped to the reaction solution that step a2 is obtained, then heat to 0 DEG C, into reaction system be added to 2 times of bromo-iodobenzene
The pure water of quality hydrolyzes 0.5~1h, is concentrated under reduced pressure, obtains product a, for use；
Step a4, the anhydrous methanol to 2 times of quality of bromo-iodobenzene is added in product a made from step a3, stirs 30min, mistake
Filter, after drying, obtains 4- bromophenyl tri-phenyl-silane.
Specific embodiment 6:
According to the preparation method of the siliceous electroluminescent organic material of one kind described in specific embodiment four, in step a1
Paradibromobenzene is replaced with to bromo-iodobenzene.
Specific embodiment 7:
According to the preparation method of the siliceous electroluminescent organic material of one kind described in specific embodiment four, in step b
The synthetic method for the halogen aryl boric acid that 4- bromophenyl tri-phenyl-silane and contraposition replace, includes the following steps:
It step b1, is that 1:1.1:2.5:0.001 weighs 4- bromophenyl tri-phenyl-silane respectively, contraposition replaces according to molar ratio
Halogen aryl boric acid, potassium carbonate, four-triphenylphosphines-palladium, for use；
Step b2, the weighed 4- bromophenyl tri-phenyl-silane of step b1 is dissolved in toluene, obtains 4- in alcohol mixed solvent
The mass ratio of bromophenyl tri-phenyl-silane mixed solution, the 4- bromophenyl tri-phenyl-silane and toluene, ethyl alcohol is 1:10:
1.5, the weighed potassium carbonate of step b1 is dissolved in pure water, the concentration of dissolved wet chemical is 2.5mol/L, will
Wet chemical is added in the 4- bromophenyl tri-phenyl-silane mixed solution, adds the weighed contraposition of step b1 and replaces
Halogen aryl boric acid, under the protection of nitrogen, stirring be warming up to 70 DEG C of micro- reflux, after being then cooled to 65 DEG C be added step b1 claim
Four-triphenylphosphines-the palladium taken obtains reaction solution b, for use in 72~73 DEG C of 4~5h of back flow reaction；
Step b3, the pure water of 1 times of volume is added in the reaction solution b for obtaining step b2, and organic layer is 60~70 after dividing water
Silicagel column is crossed under the conditions of DEG C, after efflux steams the toluene of 3/4 times of volume, is rapidly added 3 times of ethyl alcohol, is cooled down under stirring condition
To 15 DEG C, filtering after drying, obtains the synthetic product of the halogen aryl boric acid of 4- bromophenyl tri-phenyl-silane and contraposition substitution.
Specific embodiment 8:
According to the preparation method of the siliceous electroluminescent organic material of one kind described in specific embodiment four, in step b1
The halogen aryl boric acid that contraposition replaces is to chlorophenylboronic acid.
Specific embodiment 9:
According to the preparation method of the siliceous electroluminescent organic material of one kind described in specific embodiment four, in step c
The synthetic method of aryl halides and 9,9- alkyl -2- aminofluorene compound, includes the following steps:
It step c1, is that 1:0.95:0.001:0.004:1.5 weighs aryl halides, 9,9- alkyl-respectively according to molar ratio
2- aminofluorene compound, Pd2(DBA)3, tert-butyl phosphine, sodium tert-butoxide, for use；
Step c2, the weighed aryl halides of step c1 are dissolved in toluene solvant, the aryl halides with it is described
Toluene mass ratio be 1:10, then add load weighted 9, the 9- alkyl -2- aminofluorene compound of step c1, Pd2
(DBA)3, tert-butyl phosphine, sodium tert-butoxide be warming up to reflux under nitrogen protection, react 2~4h, obtain reaction solution c, for use；
Step c3, the pure water of 1 times of volume is added in the reaction solution c for obtaining step c2, and organic layer is 60~70 after dividing water
Silicagel column is crossed under the conditions of DEG C, after efflux steams the toluene of 3/5 times of volume, is rapidly added 3 times of isopropanol, stirring condition decline
For temperature to 15 DEG C, filtering after drying, obtains the synthetic product of aryl halides Yu 9,9- alkyl -2- aminofluorene compound.
Specific embodiment 10:
According to the preparation method of the siliceous electroluminescent organic material of one kind described in specific embodiment four, in step c1
Aryl halides are 4- bromo biphenyl, and 9,9- alkyl -2- aminofluorene compounds are 9,9- dimethyl -2- amino substance.
Specific embodiment 11:
According to the preparation method of the siliceous electroluminescent organic material of one kind described in specific embodiment four, in step d
R1 is the synthetic method of the siliceous electroluminescent organic material of described one kind of unsubstituted, is included the following steps:
Step d1, the 4- bromophenyl of step a preparation is weighed respectively for 1:0.95:0.001:0.004:1.5 according to molar ratio
Synthetic product, the Pd of tri-phenyl-silane, the aryl halides of step c preparation and 9,9- alkyl -2- aminofluorene compound2(DBA)3、
Tert-butyl phosphine, sodium tert-butoxide, for use；
Step d2, the weighed 4- bromophenyl tri-phenyl-silane of step d1 is dissolved in toluene solvant, the 4- bromophenyl
The mass ratio of tri-phenyl-silane and the toluene is 1:10, then adds the load weighted aryl halides of step d1 and 9,9-
Synthetic product, the Pd of alkyl -2- aminofluorene compound2(DBA)3, tert-butyl phosphine, sodium tert-butoxide be warming up under nitrogen protection
Reflux reacts 2~4h, obtains reaction solution d, for use；
Step d3, the pure water of 1 times of volume is added in the reaction solution d for obtaining step d2, and organic layer is 60~70 after dividing water
Silicagel column is crossed under the conditions of DEG C, after efflux steams the toluene of 3/5 times of volume, is rapidly added 3 times of isopropanol, stirring condition decline
Temperature is to 15 DEG C, filtering, after drying, obtains the siliceous electroluminescent organic material of described one kind of unsubstituted.
Specific embodiment 12:
According to the preparation method of the siliceous electroluminescent organic material of one kind described in specific embodiment four, in step e
R1 is the synthetic method of the siliceous electroluminescent organic material of described one kind of substituted base, is included the following steps:
Step e1, the 4- bromophenyl of step b preparation is weighed respectively for 1:0.95:0.001:0.004:1.5 according to molar ratio
Aryl halides and 9,9- alkyl -2- prepared by synthetic product, the step c for the halogen aryl boric acid that tri-phenyl-silane and contraposition replace
Synthetic product, the Pd of aminofluorene compound2(DBA)3, tert-butyl phosphine, sodium tert-butoxide, for use；
Step e2, the synthesis for the halogen aryl boric acid that the weighed 4- bromophenyl tri-phenyl-silane of step e1 and contraposition replace is produced
Object is dissolved in toluene solvant, the synthetic product of the halogen aryl boric acid of the 4- bromophenyl tri-phenyl-silane and contraposition substitution and institute
The mass ratio for the toluene stated is 1:10, then adds the load weighted aryl halides of step e1 and 9,9- alkyl -2- aminofluorene
Synthetic product, the Pd of compound2(DBA)3, tert-butyl phosphine, sodium tert-butoxide be warming up to reflux under nitrogen protection, reaction 2~
4h obtains reaction solution e, for use；
Step e3, the pure water of 1 times of volume is added in the reaction solution e for obtaining step e2, and organic layer is 60~70 after dividing water
Silicagel column is crossed under the conditions of DEG C, after efflux steams the toluene of 3/5 times of volume, is rapidly added 3 times of isopropanol, stirring condition decline
Temperature is to 15 DEG C, filtering, after drying, obtains the siliceous electroluminescent organic material of described one kind of substituted base.
Claims (10)
1. a kind of siliceous electroluminescent organic material, it is characterised in that: the siliceous electroluminescent organic material of described one kind
General structure are as follows:
Wherein, R1 group are as follows: unsubstituted or aryl or xenyl；R2 group are as follows: aryl or xenyl or naphthalene；R3 group
Structural formula is
2. a kind of preparation method for the electroluminescent organic material that one kind described in claim 1 is siliceous, it is characterised in that: including
Following steps:
Step a, it the synthesis of 4- bromophenyl tri-phenyl-silane: is prepared by tri-phenyl chloride with to bromo-iodobenzene, for use；
Step b, the synthesis for the halogen aryl boric acid that 4- bromophenyl tri-phenyl-silane and contraposition replace: 4- bromophenyl triphenyl silicon is obtained
The synthetic product for the halogen aryl boric acid that alkane and contraposition replace；
Step c, the synthesis of aryl halides and 9,9- alkyl -2- aminofluorene compound, obtains aryl halides and 9,9- alkyl -
The synthetic product of 2- aminofluorene compound；
Step d, R1 is a kind of synthesis of siliceous electroluminescent organic material of unsubstituted；
Step e, R1 is a kind of synthesis of siliceous electroluminescent organic material of substituted base.
3. the preparation method of the siliceous electroluminescent organic material of one kind according to claim 2, it is characterised in that: step
The synthetic method of 4- bromophenyl tri-phenyl-silane, includes the following steps: in a
It step a1, is that 1:1:1 is weighed to bromo-iodobenzene, butyl lithium, tri-phenyl chloride, for use respectively according to molar ratio；
Step a2, under the protection of nitrogen, tetrahydrofuran solvent is added under stirring conditions to bromo-iodobenzene by step a1 is weighed,
The mass ratio to bromo-iodobenzene and the tetrahydrofuran is then 1:6 is cooled to -80~-75 DEG C, a dropping step a1
Weighed butyl lithium reacts 1~2 hour at -80~-75 DEG C after dropwise addition, obtains reaction solution, for use；
Step a3, the weighed tri-phenyl chloride of step a1 is added tetrahydrofuran solvent under stirring conditions, described three
The mass ratio of phenyl chlorosilane and the tetrahydrofuran is 1:3, and obtained mixed solution is under the protection of nitrogen, stirring condition
Under be slowly dropped to the reaction solution that step a2 is obtained, then heat to 0 DEG C, into reaction system be added to 2 times of quality of bromo-iodobenzene
Pure water, hydrolyze 0.5~1h, be concentrated under reduced pressure, obtain product a, for use；
Step a4, the anhydrous methanol to 2 times of quality of bromo-iodobenzene is added in product a made from step a3, stirs 30min, filtered, dried
After dry, 4- bromophenyl tri-phenyl-silane is obtained.
4. the preparation method of the siliceous electroluminescent organic material of one kind according to claim 3, it is characterised in that: step
Paradibromobenzene is replaced with to bromo-iodobenzene in a1.
5. the preparation method of the siliceous electroluminescent organic material of one kind according to claim 2, it is characterised in that: step
The synthetic method for the halogen aryl boric acid that 4- bromophenyl tri-phenyl-silane and contraposition replace in b, includes the following steps:
Step b1,4- bromophenyl tri-phenyl-silane is weighed respectively for 1:1.1:2.5:0.001 according to molar ratio, the halogen that contraposition replaces
Stand-by step b2, the weighed 4- bromophenyl tri-phenyl-silane of step b1 is dissolved in by aryl boric acid, potassium carbonate, tetra-triphenylphosphine palladium
Obtain 4- bromophenyl tri-phenyl-silane mixed solution in toluene, alcohol mixed solvent, the 4- bromophenyl tri-phenyl-silane with
Toluene, ethyl alcohol mass ratio be 1:10:1.5, the weighed potassium carbonate of step b1 is dissolved in pure water, dissolved potash water
The concentration of solution is 2.5mol/L, wet chemical will be added in the 4- bromophenyl tri-phenyl-silane mixed solution, then
The halogen aryl boric acid that the weighed contraposition of step b1 replaces is added, under the protection of nitrogen, stirring is warming up to 70 DEG C of micro- reflux, then
The weighed tetra-triphenylphosphine palladium of step b1 is added after being cooled to 65 DEG C and obtains reaction solution b in 72~73 DEG C of 4~5h of back flow reaction,
For use；
Step b3, the pure water of 1 times of volume is added in the reaction solution b for obtaining step b2, and organic layer is in 60~70 DEG C of items after dividing water
After part descended silicagel column, efflux to steam the toluene of 3/4 times of volume, it is rapidly added 3 times of ethyl alcohol, is cooled to 15 under stirring condition
DEG C, filtering after drying, obtains the synthetic product of the halogen aryl boric acid of 4- bromophenyl tri-phenyl-silane and contraposition substitution.
6. the preparation method of the siliceous electroluminescent organic material of one kind according to claim 5, it is characterised in that: step
It is to chlorophenylboronic acid that substituted halogen aryl boric acid is aligned in b1.
7. the preparation method of the siliceous electroluminescent organic material of one kind according to claim 2, it is characterised in that: step
The synthetic method of aryl halides and 9,9- alkyl -2- aminofluorene compound, includes the following steps: in c
It step c1, is that 1:0.95:0.001:0.004:1.5 weighs aryl halides, 9,9- alkyl -2- ammonia respectively according to molar ratio
Base fluorene compound, Pd2(DBA)3, tert-butyl phosphine, sodium tert-butoxide, for use；
Step c2, the weighed aryl halides of step c1 are dissolved in toluene solvant, the aryl halides and the first
The mass ratio of benzene is 1:10, then adds load weighted 9, the 9- alkyl -2- aminofluorene compound of step c1, Pd2(DBA)3, uncle
Butyl phosphine, sodium tert-butoxide are warming up to reflux under nitrogen protection, react 2~4h, obtain reaction solution c, for use；
Step c3, the pure water of 1 times of volume is added in the reaction solution c for obtaining step c2, and organic layer is in 60~70 DEG C of items after dividing water
After part descended silicagel column, efflux to steam the toluene of 3/5 times of volume, it is rapidly added 3 times of isopropanol, is cooled under stirring condition
15 DEG C, filtering after drying, obtains the synthetic product of aryl halides Yu 9,9- alkyl -2- aminofluorene compound.
8. the preparation method of the siliceous electroluminescent organic material of one kind according to claim 7, it is characterised in that: step
Aryl halides are 4- bromo biphenyl in c1, and 9,9- alkyl -2- aminofluorene compounds are 9,9- dimethyl -2- amino substance.
9. the preparation method of the siliceous electroluminescent organic material of one kind according to claim 2, it is characterised in that: step
R1 is a kind of synthetic method of siliceous electroluminescent organic material of unsubstituted in d, is included the following steps:
Step d1, the 4- bromophenyl triphen of step a preparation is weighed respectively for 1:0.95:0.001:0.004:1.5 according to molar ratio
Synthetic product, the Pd of base silane, the aryl halides of step c preparation and 9,9- alkyl -2- aminofluorene compound2(DBA)3, tertiary fourth
Base phosphine, sodium tert-butoxide, for use；
Step d2, the weighed 4- bromophenyl tri-phenyl-silane of step d1 is dissolved in toluene solvant, the 4- bromophenyl triphen
The mass ratio of base silane and the toluene is 1:10, then adds the load weighted aryl halides of step d1 and 9,9- alkane
Synthetic product, the Pd of base -2- aminofluorene compound2(DBA)3, tert-butyl phosphine, sodium tert-butoxide be warming up to back under nitrogen protection
Stream reacts 2~4h, obtains reaction solution d, for use；
Step d3, the pure water of 1 times of volume is added in the reaction solution d for obtaining step d2, and organic layer is in 60~70 DEG C of items after dividing water
After part descended silicagel column, efflux to steam the toluene of 3/5 times of volume, it is rapidly added 3 times of isopropanol, is cooled under stirring condition
15 DEG C, filtering after drying, obtains the siliceous electroluminescent organic material of described one kind of unsubstituted.
10. the preparation method of the siliceous electroluminescent organic material of one kind according to claim 2, it is characterised in that: step
R1 is a kind of synthetic method of siliceous electroluminescent organic material of substituted base in rapid e, is included the following steps:
Step e1, the 4- bromophenyl triphen of step b preparation is weighed respectively for 1:0.95:0.001:0.004:1.5 according to molar ratio
Aryl halides and 9,9- alkyl -2- amino prepared by synthetic product, the step c for the halogen aryl boric acid that base silane and contraposition replace
Synthetic product, the Pd of fluorene compound2(DBA)3, tert-butyl phosphine, sodium tert-butoxide, for use；
Step e2, the weighed 4- bromophenyl tri-phenyl-silane of step e1 and the synthetic product of the halogen aryl boric acid of contraposition substitution is molten
In toluene solvant, the synthetic product of halogen aryl boric acid that the 4- bromophenyl tri-phenyl-silane and contraposition replace and described
The mass ratio of toluene is 1:10, then adds the load weighted aryl halides of step e1 and 9,9- alkyl -2- aminofluorene chemical combination
Synthetic product, the Pd of object2(DBA)3, tert-butyl phosphine, sodium tert-butoxide be warming up to reflux under nitrogen protection, react 2~4h, obtain
To reaction solution e, for use；
Step e3, the pure water of 1 times of volume is added in the reaction solution e for obtaining step e2, and organic layer is in 60~70 DEG C of items after dividing water
After part descended silicagel column, efflux to steam the toluene of 3/5 times of volume, it is rapidly added 3 times of isopropanol, is cooled under stirring condition
15 DEG C, filtering after drying, obtains the siliceous electroluminescent organic material of described one kind of substituted base.
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