CN107513075A - The carbazole compound and its preparation of boron containing diaryl and triphenylethylene structure - Google Patents
The carbazole compound and its preparation of boron containing diaryl and triphenylethylene structure Download PDFInfo
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- CN107513075A CN107513075A CN201710796252.3A CN201710796252A CN107513075A CN 107513075 A CN107513075 A CN 107513075A CN 201710796252 A CN201710796252 A CN 201710796252A CN 107513075 A CN107513075 A CN 107513075A
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- carbazole
- boron containing
- triphenylethylene
- carbazole compound
- compound
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- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 title claims abstract description 46
- MKYQPGPNVYRMHI-UHFFFAOYSA-N Triphenylethylene Chemical group C=1C=CC=CC=1C=C(C=1C=CC=CC=1)C1=CC=CC=C1 MKYQPGPNVYRMHI-UHFFFAOYSA-N 0.000 title claims abstract description 27
- -1 carbazole compound Chemical class 0.000 title claims abstract description 26
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 22
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 125000000707 boryl group Chemical group B* 0.000 claims abstract description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 11
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 10
- 239000012965 benzophenone Substances 0.000 claims abstract description 4
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- 239000010410 layer Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000005401 electroluminescence Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 5
- 239000012044 organic layer Substances 0.000 claims description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000008366 benzophenones Chemical class 0.000 claims description 3
- 238000006073 displacement reaction Methods 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 17
- 239000011368 organic material Substances 0.000 abstract description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract 2
- 229910052794 bromium Inorganic materials 0.000 abstract 2
- MUYDWENDBSDTJH-UHFFFAOYSA-N 1-(1,2,2-triphenylethenyl)-9H-carbazole Chemical class C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=2NC3=CC=CC=C3C=2C=CC=1)C1=CC=CC=C1 MUYDWENDBSDTJH-UHFFFAOYSA-N 0.000 abstract 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 description 10
- 230000008020 evaporation Effects 0.000 description 10
- 239000007787 solid Substances 0.000 description 8
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 150000001336 alkenes Chemical group 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 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 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/027—Organoboranes and organoborohydrides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention provides the carbazole compound and its preparation of a kind of boron containing diaryl and triphenylethylene structure and application.The compound is 9 ethyl 3 (4 (two (2,4,6 trimethylphenyl) boryls) phenyl) 6 (1,2,2 triphenyl vinyl) carbazoles.Its preparation method：It is sequentially prepared the carbazyl Benzophenone of 9 ethyl, 6 bromine 3,9 ethyl 3 bromine 6 (1,2,2 triphenyl vinyl) carbazole；Then by the bromine 6 (1 of 9 ethyl 3,2,2 triphenyl vinyls) carbazole and 4 (two (2,4,6 trimethylphenyls) boryl) phenyl boric acid reacts to obtain (4 (two (2,4,6 trimethylphenyl) boryls) phenyl) 6 (1 of 9 ethyl 3,2,2 triphenyl vinyls) carbazole.The compound has excellent thermal stability, electrochemically stable performance, charge transport properties and luminescent properties, can be used as blue-green electroluminescent organic material.
Description
Technical field
The present invention relates to carbon containing, hydrogen, nitrogen, boron heterocyclic compound, particularly belong to a kind of boron containing diaryl and triphenyl second
The preparation method of the carbazole compound of alkene structure, and application of the compound as electroluminescent organic material.
Background technology
In recent decades, Organic Light Emitting Diode (OLEDs) is because it is in full color flat-panel monitor and solid-state illumination
Potentiality and cause sizable concern.In OLED, luminescent material plays an important role in the aspect of performance of device.So
And when as film, most of traditional luminescent materials are typically non-luminescent or weak transmitting, because in the collected state,
Because the interaction of intermolecular pi-pi accumulation is strong and radiationless decay occurs, this phenomenon, which is referred to as aggregation, to be caused to be quenched
(ACQ).This loyalty of Tang et al. proposes a kind of interesting method for overcoming ACQ, referred to as aggregation-induced emission (AIE).Due to activity
Internal Rotations of Molecules process, the fluorescence intensity of AIE compounds is very low in dilute concentration, but in poor solvent, be prepared into film or poly-
Intensity increases rapidly when integrating as nano particle.Because aggregation of the fluorescence molecule in solid phase is spontaneous process, therefore develop this
Kind AIE systems are significant.
After AIE phenomenons are suggested to, the study mechanism of AIE molecules causes the interest of many research institutions.Tang Benzhong
It is obstructed mechanism (RIR) etc. Internal Rotations of Molecules is proposed.AIE molecules usually contain the structure with molecule rotor, and when complete
During solvation, the excited energy of molecule is consumed by the rotation of rotor, and energy is decayed rapidly without launching.After polymerization, AIE molecules
Between intermolecular interaction limitation rotor rotation, cause molecule to return to ground state by way of radiative decay, so as to send out
Penetrate strong light.The discovery of AIE phenomenons is for luminescent material of the system design with High Efficiency Solid-State fluorescence efficiency with far reaching significance.
In OLED, the organic fluorescence materials with High Efficiency Solid-State fluorescence radiation efficiency are necessary, and AIE materials are then
It is the most promising candidate of these applications.In many AIE materials, triphenylethylene molecule and its derivative are due to letter
Monostable molecular structure, easy synthesis step and significant AIE effects and furtherd investigate.The three of triphenylethylene molecule
Individual phenyl ring and center alkene plane have about 50 ° of a twist angle, this propeller-like conformation can effective ground resistance stop pi-pi accumulation and make
With this is it is prevented that luminous red shift in non-radiative decay and conventional crystalline；In addition, in crystal in a triphenylethylene molecule
Hydrogen atom can form polytype C-H ... π hydrogen bonds, these molecules between the pi-electron of adjacent triphenylethylene molecule phenyl ring
Between hydrogen bond can further lock and the conformation of stable triphenylethylene.All these, which are acted on, causes triphenylethylene to have in the solid state by force
It is strong luminous.In addition, diaryl boron group is as a kind of electron acceptor unit, low p on its boron central atomπUnoccupied orbital, favorably
In the electronic transmission performance of enhancing molecule, while large volume, the space steric effect of twist structured diaryl boron group also have
Help eliminate ACQ effects, improve solid luminescent efficiency, diaryl boron group is cleverly incorporated into the body of triphenylethylene and carbazole
By the great efficiency for improving device in system.Therefore, the research tool for boron containing diaryl and the carbazole compound of triphenylethylene
There is far reaching significance.The MOLECULE DESIGN of this kind of compound is we provided herein, is prepared, optical and electronic property.
The content of the invention
It is an object of the invention to provide a kind of boron containing diaryl and the carbazole compound and its system of triphenylethylene structure
Preparation Method.
Another object of the present invention is to provide a kind of carbazole compound work of boron containing diaryl and triphenylethylene structure
The application for being luminescent material in organic electroluminescence device.
The carbazole compound of a kind of boron containing diaryl provided by the invention and triphenylethylene structure, it is 9- ethyls -3-
(4- (two-(2,4,6- trimethylphenyl) boryls) phenyl) -6- (1,2,2- triphenyl vinyl) carbazole (DBPTECZ), structure
Formula is：
The reaction equation of preparation boron containing diaryl provided by the invention and the carbazole compound of triphenylethylene structure is as follows：
Compound DBPTECZ preparation method, comprises the following steps：
(1) in molar ratio 1：1.2 take 9- ethyls -3- bromines carbazole and chlorobenzoyl chloride, add CH2Cl2；Then, it is being passed through nitrogen
Under, aluminium chloride is slowly added into said mixture；Reaction keeps 6h at 40 DEG C；After being cooled to room temperature, extract, wash, do
Dry, then pillar layer separation, obtains compound (the bromo- 3- carbazyls Benzophenones of 9- ethyls -6- of white solid；
(2) take in agitating solution of the diphenyl methane in anhydrous THF, at 0 DEG C, under nitrogen atmosphere, be added dropwise identical mole
N-BuLi；Mixture is stirred into 1.5h at 0 DEG C, is then slowly added into compound 1 (with diphenyl methane mol ratio 1：
1.2)；It will react back after being warmed to room temperature 18h；Then, NH is used4Reaction, CH is quenched in the Cl aqueous solution2Cl2Extraction；Dry, be heated to reflux
6h；After mixture is cooled into room temperature, evaporation, NaHCO is used3The aqueous solution washs, and uses CH2Cl2Extraction, with anhydrous MgSO4Dry；
Pillar layer separation, obtain compound 9- ethyls -3- bromo- 6- (1,2,2- triphenyl vinyl) carbazole of greenish yellow solid；
(3) in molar ratio 1:1.5:0.03:4 take 9- ethyls -3- bromo- 6- (1,2,2- triphenyl vinyls) carbazole, 4-
(two-(2,4,6- trimethylphenyls) boryls) phenyl boric acid, Pd (PPh3)4And K2CO3It is placed in the container with agitator；Will be anti-
System is answered to take out air and with nitrogen displacement 2-3 times；Then mixed solvent water and THF (volume ratios 1 are added:1.3)；Mixture is existed
It is passed through stirred under nitrogen backflow 20-30h；Reaction terminating and after being cooled to room temperature, reactant mixture CH2Cl2Extraction；Organic layer
It is washed with water, then with anhydrous MgSO4Dry；Finally by post separation obtain yellow product 9- ethyls -3- (4- (two-(2,4,
6- trimethylphenyls) boryl) phenyl) -6- (1,2,2- triphenyl vinyls) carbazole.
Described boron containing diaryl and the carbazole compound of triphenylethylene structure can be used as blue-green organic electroluminescent
Material.
A kind of organic electroluminescence device provided by the invention, including luminescent layer, described luminescent layer contain described contain
The carbazole compound of diaryl boron and triphenylethylene structure.
The device that we prepare is blue organic electroluminescent device, and device architecture is：ITO/NPB (thickness 50nm)/CPB
(thickness 50nm)/DBPTECZ (thickness 50nm)/Bphen (thickness 20nm/LiF (thickness 0.5nm)/Al (thickness 150nm).
Luminescent device provided by the invention test indicate that：The cut-in voltage of luminescent device is 6.2V, and high-high brightness is
21054cd/m-2, maximum lumen efficiency is 3.34cd/A-1.It is hair excellent in organic electroluminescence device to illustrate the compound
Luminescent material, it is with a wide range of applications.
Compared with prior art, the present invention has the advantage that and effect：
1. boron containing diaryl and the carbazole compound of triphenylethylene structure that the present invention synthesizes, good with heat endurance,
The characteristics of luminous efficiency is high, luminescent material can be used as.
2. the simple synthetic method of boron containing diaryl provided by the invention and the carbazole compound of triphenylethylene structure, production
Produce rate and purity are high, and operation is easy.
3. boron containing diaryl provided by the invention and the carbazole compound of triphenylethylene structure can be used as organic electroluminescence hair
Blue emitting material in optical device, has broad application prospects.
Brief description of the drawings
Fig. 1 compounds DBPTECZ ultra-violet absorption spectrum
Fig. 2 compounds DBPTECZ fluorescence spectra
Fig. 3 compounds DBPTECZ AIE luminescent spectrums
Fig. 4 compounds DBPTECZ solid state fluorescence luminescent spectrum
Current density-voltage-brightness curve of Fig. 5 luminescent devices
Current efficiency-current density plot of Fig. 6 luminescent devices
The electroluminescent spectrum of Fig. 7 luminescent devices
Embodiment
Embodiment 1.9- ethyls -3- (4- (two-(2,4,6- trimethylphenyls) boryls) phenyl) -6- (1,2,2- triphenyls
Vinyl) carbazole preparation, step is as follows：
(1) synthesis of the bromo- 3- carbazyls Benzophenones of 9- ethyls -6-
In containers of the 250mL with agitator, 9- ethyl -3- bromines carbazoles (3.57g, 13.03mmol), benzoyl are added
Chlorine (2.19g, 15.64mmol) and 60mLCH2Cl2.Then, in a nitrogen atmosphere, it is aluminium chloride (1.82g, 13.67mmol) is slow
Slowly it is added in said mixture.Reaction is kept for 6 hours at 40 DEG C.After being cooled to room temperature, cold water (200mL) is poured the mixture into
In, use CH2Cl2(3 × 50mL) is extracted.Organic layer is washed with water, and is dried with anhydrous magnesium sulfate, then evaporation solvent.Crude product leads to
Silica gel column chromatography purifying is crossed, eluant, eluent is used as using petroleum ether/dichloromethane.Obtain white solid 4.0g, yield 81%.
(2) synthesis of the bromo- 6- of 9- ethyls -3- (1,2,2- triphenyl vinyls) carbazole
Into agitating solution of the diphenyl methane (1.06mL, 6.4mmol) in anhydrous THF (40mL), at 0 DEG C, nitrogen
Under atmosphere, 4.0mL n-BuLis (1.6M hexane solutions, 4.0mL, 6.4mmol) are added dropwise.It is small that mixture is stirred at 0 DEG C to 1.5
When, it is then slowly added into compound 1 (2.0g, 5.3mmol).Reaction is recycled to room temperature 18 hours.Then, NH is used4Cl is water-soluble
Reaction is quenched in liquid, uses CH2Cl2(3 × 50mL) is extracted.Organic extract liquid is dried with anhydrous magnesium sulfate, evaporation solvent, is subsequently solubolized in
In toluene (80mL), it is heated to reflux, p-methyl benzenesulfonic acid (1.5g, 8mmol) is present 6 hours.After mixture is cooled into room temperature, steam
Hair, uses NaHCO3The aqueous solution washs, and uses CH2Cl2Extraction, with anhydrous MgSO4Dry.Then filter mixture and carry out solvent steaming
Hair.Crude product is purified by silica gel column chromatography, and eluant, eluent is used as using petroleum ether/dichloromethane.Obtain greenish yellow solid
1.5g, yield 54%.
(3) 9- ethyls -3- (4- (two-(2,4,6- trimethylphenyls) boryls) phenyl) -6- (1,2,2- triphenylethylenes
Base) carbazole synthesis and sign
In containers of the 250mL with agitator, 9- ethyls -3- bromo- 6- (1,2,2- triphenyl vinyl) carbazole is added
(0.6g, 1.14mmol), 4- (two-(2,4,6- trimethylphenyl) boryls) phenyl boric acid (0.63g, 1.7mmol), Pd (PPh3)4
(35g, 0.03mmol) and K2CO3(0.63g, 4.5mmol).Reaction system is taken out into air and with nitrogen displacement 2-3 times.Then plus
Enter 50mL THF and 15mL water.Mixture is stirred at reflux under nitrogen atmosphere 24 hours.Reaction terminating and after being cooled to room temperature, instead
Answer mixture CH2Cl2Extraction.Organic layer is washed with water, then with anhydrous MgSO4Dry.Evaporation solvent under reduced pressure, then
By silica gel chromatography, required yellow solid (DBPTECZ) 0.517g, yield 67% are obtained.
Characterize data：1H NMR (600MHz, DMSO) δ 8.33 (s, 1H), 7.82 (dd, J=23.5,15.8Hz, 4H),
7.66 (d, J=8.7Hz, 1H), 7.42 (dd, J=27.6,8.2Hz, 3H), 7.20-6.94 (m, 16H), 6.84 (s, 4H),
4.40 (q, J=7.1Hz, 2H), 2.27 (s, 6H), 1.98 (s, 12H), 1.30 (t, J=7.1Hz, 3H)13C NMR(600MHz,
CDCl3)δ(ppm):140.85,138.46,137.26,131.57,131.53,131.48,129.92,128.15,127.68,
127.64,126.56,126.19,126.14,125.10,119.21,108.71,107.72,37.74,23.53,21.25,
13.91.
Structure, preparation and the performance of the organic electroluminescence device of embodiment 2.：
The device that we prepare is blue organic electroluminescent device, and device architecture is：ITO/NPB (thickness 50nm)/CPB
(thickness 50nm)/compound DBPTECZ (thickness 50nm)/Bphen (thickness 20nm)/LiF (thickness 0.5nm)/Al (thickness
150nm).Wherein, NPB is as hole mobile material；CPB is as electron-blocking materials；9- ethyls -3- (4- (two-(2,4,6- tri-
Aminomethyl phenyl) boryl) phenyl) -6- (1,2,2- triphenyl vinyls) carbazole (compound DBPTECZ) is used as luminescent layer；Bphen
As electron transfer layer.
The preparation process of device：Ito glass is cleaned, first ito glass is cleaned with acetone, then, is rinsed with clear water, then again
It is cleaned by ultrasonic with cleaning fluid, then is washed with clear water ultrasound.Clean substrate is dried up with nitrogen, finally with ultraviolet-ozone handle with
Fully clean surface.The thick NPB of 50nm are deposited as empty on ITO substrates according to the structure of designed device successively in order
Cave transport layer, evaporation 50nm thick CPB is as electron-blocking materials, 9- ethyls -3- (4- (two-(2,4,6- thick evaporation 50nm
Trimethylphenyl) boryl) phenyl) -6- (1,2,2- triphenyl vinyl) carbazole (compound DBPTECZ) is used as luminescent layer, steams
150nm thickness is deposited as electron injecting layer as electron transfer layer, lithium fluoride thick evaporation 0.5nm in Bphen thick plating 20nm
Negative electrode of the aluminium as device.Whole evaporation process is carried out under a high vacuum, and the evaporation rate of organic layer is controlled in 0.2-
0.5nm/s, the evaporation rate of metallic aluminum are controlled in 0.5-1nm/s.
Luminescent device provided by the invention test indicate that：Device A cut-in voltage is 6.2V, and high-high brightness is
21054cd/m-2, maximum lumen efficiency is 3.34cd/A-1.Device A premium properties shows that compound DBPTECZ is Organic Electricity
Excellent luminescent material in electroluminescence device, is with a wide range of applications.
Claims (6)
1. the carbazole compound of a kind of boron containing diaryl and triphenylethylene structure, it is characterised in that structural formula is：
2. a kind of preparation method of the carbazole compound of boron containing diaryl and triphenylethylene structure as claimed in claim 1,
It is characterised in that it includes following steps：
(1) the bromo- 3- carbazyls Benzophenones of 9- ethyls -6- are prepared；
(2) 9- ethyls -3- bromo- 6- (1,2,2- triphenyl vinyls) carbazole is prepared；
(3) in molar ratio 1:1.5:0.03:4 take 9- ethyls -3- bromo- 6- (1,2,2- triphenyl vinyls) carbazole, 4- (two-(2,
4,6- trimethylphenyls) boryl) phenyl boric acid, Pd (PPh3)4And K2CO3It is placed in the container with agitator；Reaction system is taken out
Air and with nitrogen displacement 2-3 times；Then volume ratio 1 is added:1.3 water and THF；In the case where being passed through nitrogen, stir the mixture for back
Flow 20-30h；Reaction terminating and after being cooled to room temperature, reactant mixture CH2Cl2Extraction；Organic layer is washed with water, then with nothing
Water MgSO4Dry；Finally yellow product 9- ethyls -3- (4- (two-(2,4,6- trimethylphenyls) boryls) are obtained by post separation
Phenyl) -6- (1,2,2- triphenyl vinyls) carbazole.
3. boron containing diaryl and the carbazole compound of triphenylethylene structure are used as blue-green Organic Electricity as claimed in claim 1
Electroluminescent material.
4. a kind of organic electroluminescence device, including luminescent layer, it is characterised in that described luminescent layer contains such as claim 1
Described boron containing diaryl and the carbazole compound of triphenylethylene structure.
5. a kind of organic electroluminescence device, it is characterised in that the structure of device is：ITO/NPB, thickness 50nm/CPB, thickness
The carbazole compound of boron containing diaryl and triphenylethylene structure described in 50nm/ claims 1, thickness 50nm/Bphen are thick
Spend 20nm/LiF, thickness 0.5nm/Al, thickness 150nm.
6. boron containing diaryl and the carbazole compound of triphenylethylene structure are in organic electroluminescence as claimed in claim 1
Application in part.
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