CN102464650A - Organic semiconductor material containing anthracene, thiofuran and truxene and preparation method and application of organic semiconductor material - Google Patents
Organic semiconductor material containing anthracene, thiofuran and truxene and preparation method and application of organic semiconductor material Download PDFInfo
- Publication number
- CN102464650A CN102464650A CN2010105477911A CN201010547791A CN102464650A CN 102464650 A CN102464650 A CN 102464650A CN 2010105477911 A CN2010105477911 A CN 2010105477911A CN 201010547791 A CN201010547791 A CN 201010547791A CN 102464650 A CN102464650 A CN 102464650A
- Authority
- CN
- China
- Prior art keywords
- polyindenes
- anthracene
- thiophene
- semiconductor material
- organic semiconductor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 *C(*)(c(cccc1)c1-c1c(C(*)(*)c2c-3ccc(-c4ccc(-c(c5c6cccc5)c(cccc5)c5c6I)[s]4)c2)c-3c2C(*)(*)c3c4)c1c2-c3ccc4-c1ccc(-c2c(cccc3)c3c(*)c3c2cccc3)[s]1 Chemical compound *C(*)(c(cccc1)c1-c1c(C(*)(*)c2c-3ccc(-c4ccc(-c(c5c6cccc5)c(cccc5)c5c6I)[s]4)c2)c-3c2C(*)(*)c3c4)c1c2-c3ccc4-c1ccc(-c2c(cccc3)c3c(*)c3c2cccc3)[s]1 0.000 description 4
- YGPLLMPPZRUGTJ-UHFFFAOYSA-N C(c1ccccc1-c1c2C3)c1c1-c4ccccc4Cc1c2-c1c3cccc1 Chemical compound C(c1ccccc1-c1c2C3)c1c1-c4ccccc4Cc1c2-c1c3cccc1 YGPLLMPPZRUGTJ-UHFFFAOYSA-N 0.000 description 1
- SNWQUNCRDLUDEX-UHFFFAOYSA-N O=C1c2ccccc2C=C1 Chemical compound O=C1c2ccccc2C=C1 SNWQUNCRDLUDEX-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
-
- 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
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
-
- 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
- H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Luminescent Compositions (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention relates to the technical field of organic semiconductor materials, and provides an organic semiconductor material containing anthracene, thiofuran and truxene. The organic semiconductor material is a compound shown in any of structural formulae I-III, wherein A1, A2 and A3 are the same or different substituted functional groups, and are selected from any one of a hydrogen atom and an electron-withdrawing group; and R is alkyl with 1-12 carbon atoms. The invention further provides a preparation method and application of the organic semiconductor material containing anthracene, thiofuran and truxene. The organic semiconductor material containing anthracene, thiofuran and truxene has high hole and electron transport properties, high solubility, high luminous efficiency and a great application prospect in the field of photoelectricity.
Description
Technical field
The invention belongs to the organic semiconductor material technical field, be specifically related to a kind of organic semiconductor material that contains anthracene, thiophene, three polyindenes.
Background technology
Along with the development of information age, have efficient, energy-conservation, light-weight organic electroluminescent flat-panel monitor (Organic Light Emitting Diodes OLEDs) and big area white-light illuminating and more and more receive people's attention.The OLED technology is paid close attention to by the scientist in the whole world, and relevant enterprise and laboratory are all in the research and development of carrying out this technology.As a kind of new LED technology, the organic electroluminescence device with characteristics such as active illuminating, light, thin, good contrast, energy consumption are low has proposed higher requirement to material.
1987, the Tang of U.S. Eastman Kodak company and VanSlyke reported the breakthrough in the organic electroluminescent research.Because the blue light energy is the highest, material just can obtain green glow and ruddiness through several different methods as long as have preferably.So if realize application purposes such as panchromatic demonstration and illumination, blue light material is even more important in the three primary colours.Anthracene single crystal is the blue organic electroluminescent material that uses the earliest, but owing to its easy crystallization makes device unstable.Because the energy of blue light is high; The ability gap length; Efficient and stability do not have green glow and red light material good, and the carrier transmission performance of material neither be fine simultaneously, and the luminescent properties that therefore improves blue light is significant to realizing panchromatic demonstration of organic electroluminescent and solid luminescence.
Summary of the invention
The embodiment of the invention provides a kind of organic semiconductor material that contains anthracene, thiophene, three polyindenes; It is high to be intended to solve in the prior art in the organic electro-optic device energy of blue light; The ability gap length, efficient is low not good enough with stability, and the technical problem of carrier transmission performance difference.
Embodiments of the invention are achieved in that a kind of organic semiconductor material that contains anthracene, thiophene, three polyindenes, and it is the compound of any one expression in the following structural formula (I)-(III):
In the formula, A
1, A
2, A
3Be functional group identical or inequality, be selected from H or the electron-withdrawing group any one.R is C
1-C
12Alkyl.
The preparation method of the organic semiconductor material that contains anthracene, thiophene, three polyindenes that a kind of synthetic route is simple, cost is low, said preparation method comprises the steps:
Choose compd A, B, C and D that following structural formula is represented,
Wherein, X is I or Br, and R is C
1-C
12Alkyl;
Under the condition of rare gas element atmosphere and organo-metallic catalyst, compd A or B or C are carried out the Suzuiki reaction with D respectively, generate compound I, compound I I or compound III, wherein A
1, A
2And A
3Be H, its structural formula is as follows:
Under the atmosphere of inert gases protective condition, with A
1, A
2And A
3For compound I, compound I I or the compound III of H are carried out substitution reaction with the compound that electron-withdrawing group is provided respectively in organic solvent system, generate A
1, A
2Or A
3Compound I, compound I I or compound III for electron-withdrawing group.
And the above-mentioned organic semiconductor material that contains anthracene, thiophene, three polyindenes is at organic electroluminescent, organic solar batteries, organic field effect tube, organic optical storage, Application for Field such as organic non-linear optical properties and organic laser.
The organic semiconductor material that contains anthracene, thiophene, three polyindenes of the embodiment of the invention contains the anthracene structural unit, in order to prevent its recrystallize, on anthracene, introduces thiophene three polyindenes, improves the stability of luminescent material.Thiophene is a five member ring heterocyclic compound, on ring, 6 πDian Zis is arranged, and meets Huckel's rule, has aromaticity, and environmental stability is good; The cloud density of thiophene is high simultaneously, has good optical, electrical properties, and its big electron density reduces its HOMO highest occupied molecular orbital (HOMO) energy level, helps hole transport, can produce indigo plant-green glow.Three polyindenes are highly symmetric condensed-nuclei aromaticss, have rigid structure.Three polyindenes are carried out suitable chemically modified, and construct novel organic conjugate functional materials, will produce unique optics and photoelectronics behavior as structural motif.In addition; The organic semiconductor material that contains anthracene, thiophene, three polyindenes is introduced electron-withdrawing group; Help making the luminescent spectrum blue shift, the introducing of electron-withdrawing group simultaneously makes the transmission performance of electronics be improved, and helps the balance of electric charge; Have widespread use, for example this type of material is applied to the organic electroluminescent flat-panel monitor and shows efficient, stable blue coloured electroluminous performance.
Description of drawings
Fig. 1 is the structural formula of the organic semiconductor material that contains anthracene, thiophene, three polyindenes of the embodiment of the invention;
Fig. 2 is the organic semiconductor material preparing method's who contains anthracene, thiophene, three polyindenes of the embodiment of the invention a schema;
Fig. 3 is the spectrogram that adopts the organic semiconductor material that contains anthracene, thiophene, three polyindenes of the embodiment of the invention;
Fig. 4 adopts the structural representation of organic electroluminescence device of the organic semiconductor material that contains anthracene, thiophene, three polyindenes of the embodiment of the invention.
Embodiment
In order to make the object of the invention, technical scheme and advantage clearer,, the present invention is further elaborated below in conjunction with accompanying drawing and embodiment.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
See also Fig. 1, be depicted as the structural formula of the organic semiconductor material that contains anthracene, thiophene, three polyindenes of the embodiment of the invention, the concrete structure formula is described below:
Wherein, A
1, A
2, A
3Be functional group identical or inequality, select in H and the electron-withdrawing group any one, R is C
1-C
12Alkyl.
Preferably, A
1, A
2, A
3Be identical electron-withdrawing group, more preferably A
1, A
2, A
3At least a in fluorine atom, cyanic acid, aldehyde radical, nitro and the carboxyl.Because the introducing of electron-withdrawing group makes the transmission performance of electronics be improved, and helps the balance of electric charge, simultaneously, identical electron-withdrawing group helps to simplify preparation technology, reduces production costs.Particularly, R is selected from C
1-C
12Alkyl.Abovementioned alkyl can be straight chained alkyl or branched-chain alkyl.
In the organic cpds that said structure formula I-III representes, comprise anthracene, thiophene and three polyindenes.Wherein, introduce big substituting group on the anthracene, improve the stability of luminescent material.Thiophene is a five member ring heterocyclic compound, on ring, 6 πDian Zis is arranged, and meets Huckel's rule, has aromaticity, and environmental stability is good; The cloud density of thiophene is high simultaneously, has good optical, electrical properties, and its big electron density reduces its HOMO orbital energy level, helps hole transport, can produce indigo plant-green glow.Three polyindenes are highly symmetric condensed-nuclei aromaticss, are one of idealized compounds of preparation liquid crystal material, fullerene derivate and C3 type asymmetry catalysis material etc.Three polyindenes are carried out suitable chemically modified, and construct novel organic conjugate functional materials, will produce unique optics and photoelectronics behavior as structural motif.In addition, the organic semiconductor material that contains anthracene, thiophene, three polyindenes is introduced electron-withdrawing group, helps making the luminescent spectrum blue shift, and the introducing of electron-withdrawing group simultaneously makes the transmission performance of electronics be improved, and helps the balance of electric charge.R is selected from C
1-C
12Alkyl, through introducing alkyl chain, help film forming processing to improve the solubility property of material, enlarge its range of application.
See also Fig. 2, the above-mentioned preparation method who contains the organic semiconductor material of anthracene, thiophene, three polyindenes comprises the steps:
S01: the compd A, B, C and the D that provide following structural formula to represent respectively
Wherein, X is I or Br, and R is C
1-C
12Alkyl;
S02: under the condition of atmosphere of inert gases and organo-metallic catalyst, compd A or B or C are carried out the Suzuiki reaction with D respectively, generate compound I, compound I I or compound III, wherein A
1, A
2And A
3Be H, its structural formula is as follows:
S03: under the atmosphere of inert gases protective condition, with A
1, A
2And A
3For compound I, compound I I or the compound III of H are carried out substitution reaction with the compound that electron-withdrawing group is provided respectively in organic solvent system, generate A
1, A
2Or A
3Compound I, compound I I or compound III for electron-withdrawing group.
In step S01, compd A, B, C and D can directly buy from market or prepare through existing compound method.Wherein, X is I or Br, and R is selected from C
1-C
12Alkyl.Abovementioned alkyl can be straight chained alkyl or branched-chain alkyl.A
1, A
2, A
3Be substituted functional group identical or inequality, select in H and the electron-withdrawing group any one.Preferably, A
1, A
2, A
3Be identical electron-withdrawing group.Because the introducing of electron-withdrawing group makes the transmission performance of electronics be improved, and helps the balance of electric charge, simultaneously, identical electron-withdrawing group helps to simplify preparation technology, reduces production costs.
In the present embodiment, compd A, B, C prepare respectively and get, and be specific as follows:
1, the preparation of compd A
The preparation of compd A may further comprise the steps:
The first step is synthetic three polyindenes of raw material by the 1-indone, and concrete steps are following: the 1-indone is joined in the mixing solutions of acetate and concentrated hydrochloric acid, heated and stirred refluxes.Reaction is poured reaction solution in the beaker that frozen water is housed into after finishing, and has a large amount of solid precipitations to produce immediately.Precipitate water, acetone and washed with dichloromethane successively, drying obtains white solid powder three polyindenes.Its reaction scheme is following:
The preparation of three polyindenes is not limited thereto kind of a method, also can buy by the preparation of phenylpropionic acid and polyphosphoric acid or from market.
Second goes on foot, and three polyindenes is dissolved in the THF under anaerobic state, be cooled to-78 ℃, slowly is added dropwise to the hexane solution of n-Butyl Lithium, and system is got back to room temperature afterreaction 0.5h naturally.After being cooled to-78 ℃ once more, dripping halogenated alkane in this reaction system, and at room temperature react 3h.Question response adds big water gaging and reacts with quencher after just finishing, and uses dichloromethane extraction then, and rotary evaporation removes and desolvates, and obtains crude product, separate through silica gel column chromatography and purify, alkyl three polyindenes.Its reaction scheme is following:
In the 3rd step, alkyl three polyindenes are joined by CH
3COOH, H
2SO
4, H
2O, CCl
4In the solution that four kinds of compound form, be heated to 40 ℃.For example add HIO
3And I
2In preceding mixed reaction system, be heated to 80 ℃, and stirring reaction 4.5h.After reaction finishes, mixed solution cool to room temperature, suction filtration, washing.What obtain is deposited in the 2h that refluxes in the methyl alcohol, cool to room temperature, and suction filtration obtains white powder haloalkyl three polyindenes at last.Its reaction scheme is following:
2, the preparation of compd B
The preparation of compd B may further comprise the steps:
The first step is synthetic three polyindenes of raw material by the 1-indone, the first step of concrete grammar reference compound A preparation process.The preparation of three polyindenes is not limited thereto kind of a method, also can buy by the preparation of phenylpropionic acid and polyphosphoric acid or from market.
Second step, but second step of the preparation reference compound A preparation process of alkyl three polyindenes.
The 3rd step; Alkyl three polyindenes are dissolved in the methylene dichloride; Simultaneously halogenide such as n-bromo-succinimide are dissolved in the methylene dichloride, the dichloromethane solution with the n-bromo-succinimide under 0 ℃ of condition slowly splashes in the reaction system that contains alkyl three polyindenes, after dropwising; System is got back to room temperature naturally, lucifuge reaction 12h.After reaction finished, mixed solution washed with Hydrogen chloride, and the bottom organic liquor is reclaimed in extraction, drying, and rotary evaporation obtains crude product after removing and desolvating, and separates through silica gel column chromatography and purifies, and recrystallization in the mixed solvent of normal hexane and methylene dichloride obtains compd B.Its reaction scheme is following:
3, the preparation of Compound C
The preparation of Compound C may further comprise the steps:
The first step is synthetic three polyindenes of raw material by the 1-indone, the first step of concrete grammar reference compound A preparation process.The preparation of three polyindenes is not limited thereto kind of a method, also can buy by the preparation of phenylpropionic acid and polyphosphoric acid or from market.
Second step, but second step of the preparation reference compound A preparation process of alkyl three polyindenes.
In the 3rd step, alkyl three polyindenes are dissolved in the methylene dichloride, simultaneously with halogen simple substance; Like bromine; Be dissolved in the methylene dichloride, the dichloromethane solution with halogen simple substance under 0 ℃ of condition slowly splashes in the reaction system that contains alkyl three polyindenes, after the liquid bromine drips; System is got back to room temperature naturally, lucifuge reaction 12h.After reaction finished, mixed solution was removed unnecessary bromine with saturated aqueous sodium thiosulfate and saturated common salt water washing, and drying is revolved steaming except that after desolvating and obtained crude product, at ethyl alcohol recrystallization, obtains the yellow crystals product.Its reaction scheme is following:
4, the preparation of Compound D
The preparation of Compound D may further comprise the steps:
The first step, preparation 9-(thiophene-2-yl) anthracene
9-bromine anthracene is joined in the reactor drum, vacuumize, lead to nitrogen circulation and make reaction system be in anaerobic state, for example under nitrogen protection, adding is dissolved with the anhydrous tetrahydrofuran solution of 2-thienyl boric acid, the Na of tetrakis triphenylphosphine palladium
2CO
3The aqueous solution is heated to 65-70 ℃ of back flow reaction 20h with mixed solution.Reaction is poured reaction solution in the aqueous solution of saturated ammonium chloride ethyl acetate extraction three times after finishing; Organic phase is washed with sodium chloride aqueous solution, drying, and rotary evaporation obtains crude product after removing and desolvating; Separate purification through silica gel column chromatography, obtain white solid 9-(thiophene-2-yl) anthracene at last.Its reaction scheme is following:
Second step, preparation 9-(5-bromothiophene-2-yl)-anthracene
9-(thiophene-2-yl) anthracene is dissolved in the methylene dichloride; Simultaneously the n-bromo-succinimide is dissolved in the methylene dichloride; Dichloromethane solution with the n-bromo-succinimide under 0 ℃ of condition slowly splashes in the reaction flask that contains 9-(thiophene-2-yl) anthracene, splashes into Glacial acetic acid min. 99.5, lucifuge reaction 12h.After reaction finished, mixed solution washed with Hydrogen chloride, extract the bottom organic liquor, drying is revolved to steam to remove and is obtained crude product after desolvating, recrystallization in the mixed solvent of normal hexane/methylene dichloride obtains yellow solid 9-(5-bromothiophene-2-yl)-anthracene.
The 3rd step, preparation 5-(anthracene-9-yl) thiophene-2-ylboronic acid or 2-(4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes)-5-(anthracene-9-yl) thiophene
The preparation of 5-(anthracene-9-yl) thiophene-2-ylboronic acid:
9-(5-bromothiophene-2-yl)-anthracene is joined in the reaction flask, vacuumize, after the logical nitrogen circulation, make reaction system be in anaerobic state; Anhydrous tetrahydro furan is injected in nitrogen protection down, system is cooled to-78 ℃ with dry ice/acetone batch, slowly is added dropwise to the hexane solution of n-Butyl Lithium; Solid dissolves fully, under same temperature, stirs this mixture 1h, in reaction mixture, drips trimethyl borate rapidly; Temperature of reaction slowly is increased to room temperature, stirs this reaction mixture 12h.When reaction is accomplished, add hydrochloric acid soln therein, stir the mixture that forms.With frozen water cancellation reaction, the sodium-chlor washing, ethyl acetate extraction, drying is revolved steaming except that after desolvating and is obtained crude product.Recrystallization in the mixed solvent of normal hexane/methylene dichloride obtains white solid 5-(anthracene-9-yl) thiophene-2-ylboronic acid.Its reaction formula is as follows:
The preparation of 2-(4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes)-5-(anthracene-9-yl) thiophene:
9-(5-bromothiophene-2-yl)-anthracene is joined in the reaction flask, vacuumize, after the logical nitrogen circulation, make reaction system be in anaerobic state, anhydrous tetrahydro furan is injected in nitrogen protection down; System is cooled to-78 ℃ with dry ice/acetone batch, slowly is added dropwise to the hexane solution of n-Butyl Lithium, solid dissolves fully; Under same temperature, stir this mixture 1.5h, in reaction mixture, add 2-isopropoxy-4,4 rapidly; 5,5-tetramethyl--1,3; 2-two assorted oxygen pentaboranes, temperature of reaction slowly is increased to room temperature, stirs this reaction mixture 12h.When reaction is accomplished, add the saturated NaCl aqueous solution therein, chloroform extraction, anhydrous sodium sulfate drying filters, and revolves to steam except that after desolvating to obtain crude product.Separate purification through silica gel column chromatography, its reaction formula is as follows:
In step S02, rare gas element can be inactive gass such as nitrogen, argon gas, and organo-metallic catalyst is preferably the organic palladium metal catalyst system, as adopting the mixture of organic palladium catalyzer or organic palladium and organophosphorus ligand.Organic solvent can adopt organic solvents such as THF, glycol dimethyl ether, benzene, chlorobenzene or toluene.The temperature of Suzuiki reaction is 60 ℃～130 ℃, and the reaction times is generally 20-40h.Its reaction formula is as follows:
Among the step S03, compound I or compound I I or compound III are in atmosphere of inert gases and provide the reagent of electron-withdrawing group to carry out substitution reaction, generate substituted compound I, compound I I and compound III.Rare gas element can be inactive gass such as nitrogen, argon gas, provides the reagent of electron-withdrawing group can be CuCN, DMF/POCl
3, HNO
3Deng reagent.Wherein, the substituted number of electron-withdrawing group can be through different feed ratio controls.Its reaction formula is as follows:
In aforesaid method, compd A, B, C, the monomeric synthetic route of D are fairly simple and ripe, thereby reduce technical process, reduce manufacturing cost.And the Suzuki coupling reaction is a kind of very sophisticated organometallic coupling reaction, and productive rate is high, mild condition, is easy to control.
The organic semiconductor material that contains anthracene, thiophene, three polyindenes that scans present embodiment through DTA carries out the thermal performance analysis sign, and the result shows that it has excellent thermostability.In addition, the organic semiconductor material that contains anthracene, thiophene, three polyindenes of present embodiment has good solubility.Its emission wavelength is 460 ± 20nm, belongs to blue light range.
The organic semiconductor material that contains anthracene, thiophene, three polyindenes of present embodiment can be applicable to organic electroluminescent, organic solar batteries, organic field effect tube, organic optical storage, fields such as organic non-linear optical properties and organic laser.Wherein, the above-mentioned organic semiconductor material that contains anthracene, thiophene, three polyindenes during as organic electroluminescence device, can be used as luminescent layer.Be that example describes below with the organic electroluminescence device.Other is like organic light storage device; Organic non-linear optical properties and organic laser apparatus and below similar, all be with the organic semiconductor material that contains anthracene, thiophene, three polyindenes of present embodiment optical memory material, nonlinear material, laserable material or semiconductor material etc. as it.
See also Fig. 3; Show and adopt the organic electroluminescence device that contains the organic semiconductor material of anthracene, thiophene, three polyindenes in the foregoing description, it comprises glass-base 31, anode 32, hole transmission layer 33, luminescent layer 34, hole blocking layer 35, electron transfer layer 36, impact plies 37 and the negative electrode 38 that is cascading.Anode 32 can adopt tin indium oxide (abbreviating ITO as), is preferably the tin indium oxide that square resistance is 10-20 Ω/; Hole transmission layer 33 can be N, N '-two (Alpha-Naphthyl)-N, N '-phenylbenzene-4,4 '-diamines (NPB); Luminescent layer 34 comprises the organic semiconductor material that contains anthracene, thiophene, three polyindenes in the foregoing description; Hole blocking layer 35 can be 2,9-dimethyl--4,7-phenylbenzene-9,10-phenanthroline (BCP); Electron transfer layer 36 can be oxine aluminium; Impact plies 37 can adopt LiF etc., but is not limited thereto.Negative electrode 38 can be but be not limited to metal A l or Ba etc.Thereby in a specific embodiment, the organic electroluminescence device structural table is shown: glass/ITO/NPB/ contains the organic semiconductor material/BCP/8-hydroxyquinoline aluminum/LiF/Al of anthracene, thiophene, three polyindenes.Each layer can adopt existing method to form.For the substituted organic semiconductor material that contains anthracene, thiophene, three polyindenes of electrophilic, have the performance of hole and electric transmission concurrently, the son transmission that helps damming, compound at luminescent layer, can obtain high luminous efficiency.Therefore the electroluminescent device formed of the organic semiconductor material that contains anthracene, thiophene, three polyindenes of the embodiment of the invention can show as efficiently, stable blue electroluminescent devices, help the flat-panel monitor and the illuminating device of superior performance of future generation.
Below through specific embodiment illustrate the organic semiconductor material preparation method that contains anthracene, thiophene, three polyindenes with and aspect such as performance.A among the following embodiment, B, C, D can distinguish according to the method described above directly preparation and get, and certainly, also can directly buy from market in other embodiments, are not limited to this.
Embodiment one:
Present embodiment contain anthracene, thiophene, the unitary organic cpds 2-of three polyindenes (5-(anthracene-9-yl) thiophene-2-yl)-5,5 ', 10,10 ', 15,15 '-Hexaethyl three polyindenes (AT1ET) in, A
1, A
2, A
3Be all H, R is C
2H
5, its structural formula is following:
The preparation process of above-mentioned AT1ET organic semiconductor material is following:
The preparation of step 1, three polyindenes, reaction formula is as follows:
Concrete preparation process is following: 1-indone 10mmol is joined in the mixing solutions that contains acetate 8mL and concentrated hydrochloric acid 4mL, be heated to 100 ℃, stirring and refluxing 20h.Reaction is poured reaction solution in the beaker that frozen water is housed into after finishing, and has a large amount of solid precipitations to produce immediately.After precipitating successively water, acetone and washed with dichloromethane, obtain white solid powder three polyindenes, productive rate: 91%.
Test result is: EI-MS:m/z 342 (M
+).
Step 2,5,5 ', 10,10 ', 15,15 '-preparation of Hexaethyl three polyindenes, reaction formula is as follows:
Detailed process is following: three polyindene 8mmol are added in the reaction flask, vacuumize, after the logical nitrogen circulation 3 times, make reaction system be in anaerobic state; Anhydrous tetrahydro furan 50mL is injected in nitrogen protection down, system is cooled to-78 ℃ with dry ice/acetone batch, slowly is added dropwise to the hexane solution of n-Butyl Lithium 56mmol; Three polyindene solids dissolve fully; Behind about 0.5h, system is got back to room temperature naturally, reacts 0.5h again.After being cooled to-78 ℃ once more, dripping 1-bromic ether 53.8mmol in this reaction system, and at room temperature react 3h.After question response just finishes, add big water gaging with the quencher reaction and use dichloromethane extraction, revolve to steam to remove and desolvate, obtain crude product, separate purification through silica gel column chromatography; Eluent is a sherwood oil, obtain at last light yellow crystal 5,5 ', 10; 10 ', 15,15 '-Hexaethyl three polyindenes, productive rate: 72%.
Test result is: EI-MS:m/z 510 (M
+).
Step 3,2-iodo-5,5 ', 10,10 ', 15,15 '-preparation of Hexaethyl three polyindenes, reaction formula is as follows:
Detailed process is following: with 5,5 ', 10,10 ', 15,15 '-Hexaethyl three polyindene 5mmol join 15ml by CH
3COOH, H
2SO
4, H
2O, CCl
4In the solution that these four kinds of compound form, wherein, the ratio of four kinds of compounds is CH
3COOH: H
2SO4: H
2O: CCl
4=100: 5: 20: 8, be heated to 40 ℃.Add HIO
31.67mmol and I
21.67mmol in preceding mixed reaction system, be heated to 80 ℃, and stirring reaction 4.5h.After reaction finishes, mixed solution cool to room temperature, suction filtration, washing.What obtain is deposited in the 2h that refluxes in the methyl alcohol, cool to room temperature, suction filtration, obtain at last white powder 2-iodo-5,5 ', 10,10 ', 15,15 '-Hexaethyl three polyindenes.Productive rate: 67%.
Test result is: MALDI/TOF-MS:m/z:637 (M
+).
The preparation of step 4,9-(thiophene-2-yl) anthracene, reaction formula is as follows:
Detailed process is following: 10mmol joins in the reaction flask with 9-bromine anthracene; Vacuumize, after the logical nitrogen circulation 3 times; Make reaction system be in anaerobic state, nitrogen protection adds down the Na of the anhydrous tetrahydrofuran solution 50mL that is dissolved with 2-thienyl boric acid 5.5mmol, tetra-triphenylphosphine palladium 0.01mmol, 2mol/L
2CO
3Aqueous solution 34ml is heated to 65-70 ℃ of back flow reaction 20h with mixed solution.Reaction is poured reaction solution in the aqueous solution of saturated ammonium chloride ethyl acetate extraction three times after finishing; Organic phase is washed with sodium chloride aqueous solution; Drying, rotary evaporation obtain crude product after removing and desolvating, and separate through silica gel column chromatography and purify; Eluent V (sherwood oil): V (methylene dichloride)=10: 1 obtains white solid 9-(thiophene-2-yl) anthracene at last.Productive rate: 96%.
Test result is: EI-MS:m/z 260 (M
+).
The preparation of step 5,9-(5-bromothiophene-2-yl)-anthracene, reaction formula is as follows:
Detailed process is following: 9-(thiophene-2-yl) anthracene 8mmol is dissolved in the 25mL methylene dichloride; Simultaneously n-bromo-succinimide (NBS) 8mmol is dissolved in the 10mL methylene dichloride; Dichloromethane solution with NBS under 0 ℃ of condition slowly splashes in the reaction flask that contains 9-(thiophene-2-yl) anthracene; Splash into the 1ml Glacial acetic acid min. 99.5, lucifuge reaction 12h.After reaction finished, mixed solution washed with Hydrogen chloride, extract the bottom organic liquor, drying is revolved to steam to remove and is obtained crude product after desolvating, recrystallization in the mixed solvent of normal hexane/methylene dichloride obtains yellow solid 9-(5-bromothiophene-2-yl)-anthracene.Productive rate: 92%.
Test result is: EI-MS:m/z 338 (M
+).
The preparation of step 6,5-(anthracene-9-yl) thiophene-2-ylboronic acid, reaction formula is as follows:
Detailed process is following: 9-(5-bromothiophene-2-yl)-anthracene 7mmol is joined in the reaction flask, vacuumize, after the logical nitrogen circulation 3 times, make reaction system be in anaerobic state; Anhydrous tetrahydro furan (50mL) is injected in nitrogen protection down; System is cooled to-78 ℃ with dry ice/acetone batch, slowly is added dropwise to the hexane solution of n-Butyl Lithium 10.5mmol, solid dissolves fully; Under same temperature, stir this mixture 1h; In reaction mixture, drip trimethyl borate rapidly, temperature of reaction slowly is increased to room temperature, stirs this reaction mixture 12h.When reaction is accomplished, add 1mol/L hydrochloric acid soln 500ml therein, stir the mixture 3.5h that forms.With frozen water cancellation reaction, the sodium-chlor washing, ethyl acetate extraction, drying is revolved steaming except that after desolvating and is obtained crude product.Recrystallization in the mixed solvent of normal hexane/methylene dichloride obtains white solid, productive rate: 70%.
Test result is: EI-MS:m/z 304 (M
+).
Step 7,2-(5-(anthracene-9-yl) thiophene-2-yl)-5,5 ', 10,10 ', 15,15 '-preparation of Hexaethyl three polyindenes (AT1ET), reaction formula is as follows:
Detailed process is following: with 2-iodo-5,5 ', 10; 10 '; 15,15 '-Hexaethyl three polyindene 3mmol join in the reaction flask, vacuumize, after the logical nitrogen circulation 3 times; Make reaction system be in anaerobic state, nitrogen protection adds down the Na of the anhydrous tetrahydrofuran solution 50mL that is dissolved with 5-(anthracene-9-yl) thiophene-2-ylboronic acid 3.1mmol, tetra-triphenylphosphine palladium 0.01mmol, 2mol/L
2CO
3Aqueous solution 34ml is heated to 65-70 ℃ of back flow reaction 20h with mixed solution.Reaction is poured reaction solution in the aqueous solution of saturated ammonium chloride after finishing, ethyl acetate extraction three times, and organic phase is washed with sodium chloride aqueous solution; Drying is revolved steam to remove and is obtained crude product after desolvating, and separates through silica gel column chromatography and purifies, and eluent is V (sherwood oil): V (methylene dichloride)=12: 1; Obtain yellow solid 2-(5-(anthracene-9-yl) thiophene-2-yl)-5,5 ' at last, 10; 10 ', 15,15 '-Hexaethyl three polyindenes.Productive rate: 86%.
Test result is: MALDI/TOF-MS:m/z:768 (M+).
Embodiment two:
Present embodiment contain anthracene, thiophene, the unitary organic cpds 2 of three polyindenes, 7-two (5-(anthracene-9-yl) thiophene-2-yl)-5,5 ', 10,10 ', 15,15 '-Hexaethyl three polyindenes (AT2ET) multipolymer, wherein, A
1, A
2, A
3Be all H, R is C
2H
5, its structural formula is following:
The preparation process of above-mentioned AT2ET organic semiconductor material is following:
Step 1,2,7-two bromo-5,5 ', 10,10 ', 15,15 '-preparation of Hexaethyl three polyindenes, reaction formula is as follows:
Detailed process is following: with 5,5 ', 10,10 '; 15,15 '-Hexaethyl three polyindene 5mmol are dissolved in the 25mL methylene dichloride, simultaneously NBS 10.5mmol are dissolved in the 10mL methylene dichloride, and under 0 ℃ of condition, the dichloromethane solution of NBS slowly splashed into and contain 5; 5 ', 10,10 ', 15; 15 '-reaction vessel of Hexaethyl three polyindenes in, splash into the 1ml Glacial acetic acid min. 99.5, lucifuge reaction 12h.After reaction finished, mixed solution washed with Hydrogen chloride, extract the bottom organic liquor, drying; Revolve steaming and obtain crude product except that after desolvating, separate through silica gel column chromatography and purify, recrystallization in the mixed solvent of normal hexane and methylene dichloride obtains yellow crystals 2; 7-two bromo-5,5 ', 10; 10 ', 15,15 '-Hexaethyl three polyindenes.Productive rate: 43%.
Test result is: MALDI/TOF-MS:m/z:666 (M
+).
Step 2,2,7-two (5-(anthracene-9-yl) thiophene-2-yl)-5,5 ', 10,10 ', 15,15 '-preparation of Hexaethyl three polyindenes (AT2ET), reaction formula is as follows:
Detailed process is following: with 2, and 7-three bromo-5,5 '; 10,10 ', 15; 15 '-Hexaethyl three polyindene 4mmol join in the reaction flask; Vacuumize, after the logical nitrogen circulation 3 times, make reaction system be in anaerobic state, nitrogen protection adds the Na of the anhydrous tetrahydrofuran solution 50mL that is dissolved with 5-(anthracene-9-yl) thiophene-2-ylboronic acid 8.2mmol, tetra-triphenylphosphine palladium 0.01mmol, 2mol/L down
2CO
3Aqueous solution 34ml is heated to 65-70 ℃ of back flow reaction 20h with mixed solution.After reaction finishes, reaction solution is poured in the aqueous solution of saturated ammonium chloride, with ethyl acetate extraction three times, organic phase is washed with sodium chloride aqueous solution; Drying is revolved to steam to remove and is desolvated, and obtains crude product, separates through silica gel column chromatography and purifies; Eluent is V (sherwood oil): V (methylene dichloride)=10: 1, obtains yellow solid 2 at last, 7-three (5-(anthracene-9-yl) thiophene-2-yl)-5,5 '; 10,10 ', 15,15 '-Hexaethyl three polyindenes.Productive rate: 82%.
Test result is: MALDI/TOF-MS:m/z 1026 (M
+).
Embodiment three:
Present embodiment contain anthracene, thiophene, the unitary organic cpds 2,7 of three polyindenes, 12-three (5-(anthracene-9-yl) thiophene-2-yl)-5,5 ', 10,10 ', 15,15 '-Hexaethyl three polyindenes (AT3ET) in, A
1, A
2, A
3Be all H, R is C
2H
5, its structural formula is following:
The preparation process of above-mentioned AT3ET organic semiconductor material is following:
Step 1,2,7,12-three bromo-5,5 ', 10,10 ', 15,15 '-preparation of Hexaethyl three polyindenes, reaction formula is as follows:
Detailed process is following: with 5,5 ', 10,10 '; 15,15 '-Hexaethyl three polyindene 5mmol are dissolved in the 25mL methylene dichloride, simultaneously liquid bromine 1mL are dissolved in the 10mL methylene dichloride, and under 0 ℃ of condition, the dichloromethane solution of liquid bromine slowly splashed into and contain 5; 5 ', 10,10 ', 15; 15 '-reaction system of Hexaethyl three polyindenes in, after the liquid bromine dripped, system was got back to room temperature naturally, lucifuge reaction 12h.After reaction finished, mixed solution was removed unnecessary bromine with saturated aqueous sodium thiosulfate and saturated common salt water washing, and drying is revolved to steam to remove and desolvated, and obtains crude product; Recrystallization in ethanol obtains yellow crystals 2,7,12-three bromo-5,5 '; 10,10 ', 15,15 '-Hexaethyl three polyindenes.Productive rate: 91%.。
Test result is: MALDI-TOF:m/z 744 (M
+).
Step 2,2,7,12-three (5-(anthracene-9-yl) thiophene-2-yl)-5,5 ', 10,10 ', 15,15 '-preparation of Hexaethyl three polyindenes (AT3ET), reaction formula is as follows:
Detailed process is following: with 2,7, and 12-three bromo-5; 5 ', 10,10 '; 15,15 '-Hexaethyl three polyindene 3.5mmol join in the reaction flask, vacuumize, after the logical nitrogen circulation 3 times; Make reaction system be in anaerobic state, nitrogen protection adds down the Na of the anhydrous tetrahydrofuran solution 50mL that is dissolved with 5-(anthracene-9-yl) thiophene-2-ylboronic acid 11mmol, tetra-triphenylphosphine palladium 0.01mmol, 2mol/L
2CO
3Aqueous solution 34ml is heated to 65-70 ℃ of back flow reaction 20h with mixed solution.Reaction is poured reaction solution in the aqueous solution of saturated ammonium chloride after finishing, ethyl acetate extraction three times, and organic phase is washed with sodium chloride aqueous solution; Drying is revolved steam to remove and is obtained crude product after desolvating, and separates through silica gel column chromatography and purifies, and eluent is V (sherwood oil): V (methylene dichloride)=8: 1; Obtain yellow solid 2,7 at last, 12-three (5-(anthracene-9-yl) thiophene-2-yl)-5,5 '; 10,10 ', 15,15 '-Hexaethyl three polyindenes.Productive rate: 79%.
Test result is: MALDI/TOF-MS:m/z 1284 (M
+).
Embodiment four:
Present embodiment contain anthracene, thiophene, the unitary organic cpds 2,7 of three polyindenes, 12-three (5-(anthracene-9-yl) thiophene-2-yl)-5,5 ', 10,10 ', in the preparation of 15,15 '-six n-hexyls, three polyindenes (AT3HT), A
1, A
2, A
3Be all H, R is C
6H
13, its structural formula is following:
The preparation process of above-mentioned AT3HT organic semiconductor material is following:
Step 1,5,5 ', 10,10 ', the preparation of 15,15 '-six n-hexyls, three polyindenes, reaction formula is as follows:
Detailed process is following: three polyindene 8mmol are added in the reaction flask, vacuumize, after the logical nitrogen circulation 3 times, make reaction system be in anaerobic state; Anhydrous tetrahydro furan 50mL is injected in nitrogen protection down, system is cooled to-78 ℃ with dry ice/acetone batch, slowly is added dropwise to the hexane solution of n-Butyl Lithium 56mmol; Three polyindene solids dissolve fully; Behind about 0.5h, system is got back to room temperature naturally, reacts 0.5h again.After being cooled to-78 ℃ once more, dripping 1-bromo normal hexane 53.8mmol in this reaction system, and at room temperature react 3h.After question response just finishes, add big water gaging with the quencher reaction and use dichloromethane extraction, revolve and steam, obtain crude product except that desolvating; Separate to purify through silica gel column chromatography, eluent is a sherwood oil, obtain at last yellow solid 5,5 '; 10,10 ', 15,15 '-six n-hexyls, three polyindenes.Productive rate: 74%.
Test result is: MALDI-TOF:m/z 847 (M+).
Step 2,2,7,12-three bromo-5,5 ', 10,10 ', the preparation of 15,15 '-six n-hexyls, three polyindenes, reaction formula is as follows:
Detailed process is following: with 5,5 ', 10,10 '; 15,15 '-six n-hexyls, three polyindene 5mmol are dissolved in the 25mL methylene dichloride, simultaneously liquid bromine 1mL are dissolved in the 10mL methylene dichloride, under 0 ℃ of condition, the dichloromethane solution of liquid bromine are slowly splashed into and contain 5; 5 ', 10,10 ', 15; In the reaction system of 15 '-six n-hexyls, three polyindenes, after the liquid bromine dripped, system was got back to room temperature naturally, lucifuge reaction 12h.After reaction finished, mixed solution was removed unnecessary bromine with saturated aqueous sodium thiosulfate and saturated common salt water washing, and drying is revolved steaming except that after desolvating and obtained crude product, recrystallization in ethanol; Obtain yellow crystals 2,7,12-three bromo-5,5 '; 10,10 ', 15,15 '-six n-hexyls, three polyindenes.Productive rate: 93%.
Test result is: MALDI-TOF:m/z 1081 (M
+).
The preparation of step 3,2-(4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes)-5-(anthracene-9-yl) thiophene, reaction formula is as follows:
Detailed process is following: vacuumize, after the logical nitrogen circulation 3 times; Make reaction system be in anaerobic state, nitrogen protection adds 9-(5-bromothiophene-2-yl)-anthracene 7mmol down in reaction flask, injects anhydrous tetrahydro furan (80mL); System is cooled to-78 ℃ with dry ice/acetone batch; Slowly be added dropwise to the hexane solution of n-Butyl Lithium 10.5mmol, solid dissolves fully, under same temperature, stirs this mixture 1.5h.Under-78 ℃ of conditions, use then and inject 2-isopropoxy-4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaborane 12mmol, temperature of reaction slowly is increased to room temperature, stirs this reaction mixture 12h.Reaction adds the saturated NaCl aqueous solution after finishing, chloroform extraction, and anhydrous sodium sulfate drying filters, and revolves to steam except that after desolvating to obtain crude product.Separate to purify through silica gel column chromatography, eluent is V (sherwood oil): V (ETHYLE ACETATE)=12: 1, obtains pulverulent solids 2-(4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes)-5-(anthracene-9-yl) thiophene at last.Productive rate: 62%.
Test result is: EI-MS:m/z 386 (M
+).
Step 4,2,7,12-three (5-(anthracene-9-yl) thiophene-2-yl)-5,5 ', 10,10 ', the preparation of 15,15 '-six n-hexyls, three polyindenes (AT3HT), reaction formula is as follows:
Detailed process is following: with 2,7, and 12-three bromo-5,5 '; 10,10 ', 15,15 '-six n-hexyls, three polyindene 3mmol join in the reaction flask; Vacuumize, after the logical nitrogen circulation 3 times, make reaction system be in anaerobic state, nitrogen protection adds down and is dissolved with 2-(4,4; 5,5-tetramethyl--1,3, the assorted oxygen pentaboranes of 2-two)-Na of the anhydrous tetrahydrofuran solution 60mL of 5-(anthracene-9-yl) thiophene 9.5mmol, tetra-triphenylphosphine palladium 0.01mmol, 2mol/L
2CO
3Aqueous solution 40ml is heated to 65-70 ℃ of back flow reaction 20h with mixed solution.Reaction is poured reaction solution in the aqueous solution of saturated ammonium chloride after finishing, ethyl acetate extraction three times, and organic phase is washed with sodium chloride aqueous solution; Drying is revolved steam to remove and is obtained crude product after desolvating, and separates through silica gel column chromatography and purifies, and eluent is V (sherwood oil): V (methylene dichloride)=9: 1; Obtain yellow solid 2,7 at last, 12-three (5-(anthracene-9-yl) thiophene-2-yl)-5,5 '; 10,10 ', 15,15 '-six n-hexyls, three polyindenes.Productive rate: 72%.
Test result is: MALDI/TOF-MS:m/z 1618 (M
+).
Embodiment five:
Present embodiment contain anthracene, thiophene, the unitary organic cpds 2,7 of three polyindenes, 12-three (5-(anthracene-9-yl) thiophene-2-yl)-5,5 ', 10,10 ', in the preparation of 15,15 '-six n-octyls, three polyindenes (AT3OT), A
1, A
2, A
3Be all H, R is C
8H
17, its structural formula is following:
The preparation process of above-mentioned AT3OT organic semiconductor material is following:
Step 1,5,5 ', 10,10 ', the preparation of 15,15 '-six n-octyls, three polyindenes, reaction formula is as follows:
Detailed process is following: three polyindene 8mmol are added in the reaction flask, vacuumize, after the logical nitrogen circulation 3 times, make reaction system be in anaerobic state; Anhydrous tetrahydro furan 50mL is injected in nitrogen protection down, system is cooled to-78 ℃ with dry ice/acetone batch, slowly is added dropwise to the hexane solution of n-Butyl Lithium 56mmol; Three polyindene solids dissolve fully; Behind about 0.5h, system is got back to room temperature naturally, reacts 0.5h again.After being cooled to-78 ℃ once more, dripping 1-n-octane bromide 53.8mmol in this reaction system, and at room temperature react 3h.After question response just finishes, add big water gaging with the quencher reaction and use dichloromethane extraction, revolve and steam, obtain crude product except that desolvating; Separate to purify through silica gel column chromatography, eluent is a sherwood oil, obtain at last yellow solid 5,5 '; 10,10 ', 15,15 '-six n-octyls, three polyindenes.Productive rate: 70%.
Test result is: MALDI-TOF:m/z 1015 (M
+).
Step 2,2,7,12-three bromo-5,5 ', 10,10 ', the preparation of 15,15 '-six n-octyls, three polyindenes, reaction formula is as follows:
Detailed process is following: with 5,5 ', 10,10 '; 15,15 '-six n-octyls, three polyindene 5mmol are dissolved in the 25mL methylene dichloride, simultaneously liquid bromine 1mL are dissolved in the 10mL methylene dichloride, under 0 ℃ of condition, the dichloromethane solution of liquid bromine are slowly splashed into and contain 5; 5 ', 10,10 ', 15; In the reaction system of 15 '-six n-octyls, three polyindenes, after the liquid bromine dripped, system was got back to room temperature naturally, lucifuge reaction 12h.After reaction finished, mixed solution was removed unnecessary bromine with saturated aqueous sodium thiosulfate and saturated common salt water washing, and drying is revolved steaming except that after desolvating and obtained crude product, recrystallization in ethanol; Obtain yellow crystals 2,7,12-three bromo-5,5 '; 10,10 ', 15,15 '-six n-octyls, three polyindenes.Productive rate: 90%.
Test result is: MALDI-TOF:m/z 1249 (M
+).
Step 3,2,7,12-three (5-(anthracene-9-yl) thiophene-2-yl)-5,5 ', 10,10 ', the preparation of 15,15 '-six n-octyls, three polyindenes (AT3OT), reaction formula is as follows:
Detailed process is following: with 2,7, and 12-three bromo-5; 5 ', 10,10 '; 15,15 '-six n-octyls, three polyindene 3.2mmol join in the reaction flask, vacuumize, after the logical nitrogen circulation 3 times; Make reaction system be in anaerobic state, nitrogen protection adds down the Na2CO3 aqueous solution 34ml of the anhydrous tetrahydrofuran solution 50mL that is dissolved with 5-(anthracene-9-yl) thiophene-2-ylboronic acid 10mmol, tetra-triphenylphosphine palladium 0.01mmol, 2mol/L, and mixed solution is heated to 65-70 ℃ of back flow reaction 20h.Reaction is poured reaction solution in the aqueous solution of saturated ammonium chloride after finishing, ethyl acetate extraction three times, and organic phase is washed with sodium chloride aqueous solution; Drying is revolved steam to remove and is obtained crude product after desolvating, and separates through silica gel column chromatography and purifies, and eluent is V (sherwood oil): V (methylene dichloride)=10: 1; Obtain yellow solid 2,7 at last, 12-three (5-(anthracene-9-yl) thiophene-2-yl)-5,5 '; 10,10 ', 15,15 '-six n-octyls, three polyindenes.Productive rate: 77%.
Test result is: MALDI/TOF-MS:m/z 1789 (M+).
Embodiment six:
Present embodiment contain anthracene, thiophene, the unitary organic cpds 2-of three polyindenes (5-(10-cyanic acid-anthracene-9-yl) thiophene-2-yl)-5,5 ', 10,10 ', 15,15 '-preparation of Hexaethyl three polyindenes (CNAT3ET) in, A
1, A
2Be H, A
3Be the CN group, R is C
2H
5, its structural formula is following:
2-(5-(10-cyanic acid-anthracene-9-yl) thiophene-2-yl)-5,5 ', 10,10 ', 15,15 '-preparation of Hexaethyl three polyindenes (CNAT3ET), reaction formula is as follows:
Detailed process is following: at N, add 2,7 among the dinethylformamide solution 30mL, 12-three (5-(anthracene-9-yl) thiophene-2-yl)-5; 5 ', 10,10 '; 15,15 '-Hexaethyl three polyindene 1.5mmol and cuprous cyanide 3mmol, in nitrogen protection refluxed reaction 20h.Be cooled to 80 ℃ subsequently, in system, add the mixing solutions of iron(ic)chloride 3mmol, concentrated hydrochloric acid 5mL and water 5mL, stirred overnight under the room temperature behind the reaction 1h.Reaction is poured in the beaker that fills big water gaging after finishing, and filters brown precipitate, water and washing with alcohol.Water layer with the dichloromethane extraction after drying, revolve steaming, two portions solid is merged to separate through silica gel column chromatography purifies, eluent is V (sherwood oil): V (methylene dichloride)=6: 1; The final light red solid 2-(5-(10-cyanic acid-anthracene-9-yl) thiophene-2-yl)-5 that obtains; 5 ', 10,10 '; 15,15 '-Hexaethyl three polyindenes.Productive rate: 69%.
Test result is: MALDI/TOF-MS:m/z 1310 (M
+).
Embodiment seven:
Present embodiment contain anthracene, thiophene, the unitary organic cpds 2,7 of three polyindenes, 12-three (5-(10-cyanic acid-anthracene-9-yl) thiophene-2-yl)-5,5 ', 10,10 ', 15,15 '-preparation of Hexaethyl three polyindenes (CN3AT3ET) in, A
1, A
2, A
3Be all CN, R is C
2H
5, its structural formula is following:
2,7,12-three (5-(10-cyanic acid-anthracene-9-yl) thiophene-2-yl)-5,5 ', 10,10 ', 15,15 '-preparation of Hexaethyl three polyindenes (CN3AT3ET), reaction formula is as follows:
Detailed process is following: at N, add 2,7 among the dinethylformamide solution 30mL, 12-three (5-(anthracene-9-yl) thiophene-2-yl)-5; 5 ', 10,10 '; 15,15 '-Hexaethyl three polyindene 1.5mmol and cuprous cyanide 15mmol, in nitrogen protection refluxed reaction 20h.Be cooled to 80 ℃ subsequently, in system, add the mixing solutions of iron(ic)chloride 15mmol, concentrated hydrochloric acid 15mL and water 15mL, stirred overnight under the room temperature behind the reaction 1h.Reaction is poured in the beaker that fills big water gaging after finishing, and filters brown precipitate, water and washing with alcohol.Water layer with the dichloromethane extraction after drying, revolve steaming, two portions solid is merged to separate through silica gel column chromatography purifies, eluent is V (sherwood oil): V (methylene dichloride)=3: 1; Final garnet solid 2,7, the 12-three (5-(10-cyanic acid-anthracene-9-yl) thiophene-2-yl)-5 of obtaining; 5 ', 10,10 '; 15,15 '-Hexaethyl three polyindenes.Productive rate: 51%.The electroluminescent spectrum figure of product is as shown in Figure 4, and as can be seen from the figure CN3AT3ET's is transmitted in 425-500nm.
Test result is: MALDI/TOF-MS:m/z 1359 (M
+).
Embodiment eight:
Present embodiment contain anthracene, thiophene, the unitary organic cpds 2,7 of three polyindenes, 12-three (5-(10-aldehyde radical-anthracene-9-yl) thiophene-2-yl)-5,5 ', 10,10 ', 15,15 '-preparation of Hexaethyl three polyindenes (CHO3AT3ET) in, A
1, A
2, A
3Be all CHO, R is C
6H
13, its structural formula is following:
2,7,12-three (5-(10-aldehyde radical-anthracene-9-yl) thiophene-2-yl)-5,5 ', 10,10 ', 15,15 '-preparation of Hexaethyl three polyindenes (CHO3AT3ET), reaction formula is as follows:
Detailed process is following: at N, add POCl among the dinethylformamide solution 100mL
315mmol, nitrogen protection, 0 ℃ is reacted 0.5h down, adds with methylene dichloride dissolved 2,7 12-three (5-(anthracene-9-yl) thiophene-2-yl)-5; 5 ', 10,10 ', 15,15 '-Hexaethyl three polyindene 1.5mmol; In 75-80 ℃ of refluxed reaction 12h, pour reacted mixed solution in frozen water hydrolysis, use dichloromethane extraction, drying is revolved steaming except that desolvating and is obtained crude product; Separate to purify through silica gel column chromatography, eluent is V (sherwood oil): V (methylene dichloride)=1: 1, finally obtains red solid 2,7,12-three (5-(10-aldehyde radical-anthracene-9-yl) thiophene-2-yl)-5; 5 ', 10,10 ', 15,15 '-Hexaethyl three polyindenes.Productive rate: 42%.
Test result is: MALDI/TOF-MS:m/z 1368 (M
+).
Embodiment nine:
Present embodiment contain anthracene, thiophene, the unitary organic cpds 2,7 of three polyindenes, 12-three (5-(10-cyanic acid-anthracene-9-yl) thiophene-2-yl)-5,5 ', 10,10 ', the preparation of 15,15 '-six n-hexyls, three polyindenes (CN3AT3HT), A
1, A
2, A
3Be all CN, R is C
6H
13, its structural formula is following:
2,7,12-three (5-(10-cyanic acid-anthracene-9-yl) thiophene-2-yl)-5,5 ', 10,10 ', the preparation of 15,15 '-six n-hexyls, three polyindenes (CN3AT3HT), reaction formula is as follows:
Detailed process is following: at N, add 2,7 among the dinethylformamide solution 30mL, 12-three (5-(anthracene-9-yl) thiophene-2-yl)-5; 5 ', 10,10 '; 15,15 '-six n-hexyls, three polyindene 1.5mmol and cuprous cyanide 15mmol are in nitrogen protection refluxed reaction 20h.Be cooled to 80 ℃ subsequently, in system, add the mixing solutions of iron(ic)chloride 15mmol, concentrated hydrochloric acid 15mL and water 15mL, stirred overnight under the room temperature behind the reaction 1h.Reaction is poured in the beaker that fills big water gaging after finishing, and filters brown precipitate, water and washing with alcohol.Water layer with the dichloromethane extraction after drying, revolve steaming, two portions solid is merged to separate through silica gel column chromatography purifies, eluent is V (sherwood oil): V (methylene dichloride)=4: 1; Final garnet solid 2,7, the 12-three (5-(10-cyanic acid-anthracene-9-yl) thiophene-2-yl)-5 of obtaining; 5 ', 10,10 '; 15,15 '-six n-hexyls, three polyindenes.Productive rate: 53%.
Test result is: MALDI/TOF-MS:m/z 1696 (M
+).
Embodiment ten:
Present embodiment contain anthracene, thiophene, the unitary organic cpds 2,7 of three polyindenes, 12-three (5-(10-aldehyde radical-anthracene-9-yl) thiophene-2-yl)-5,5 ', 10,10 ', the preparation of 15,15 '-six n-octyls, three polyindenes (CHO3AT3OT), A
1, A
2, A
3Be all CHO, R is C
8H
17, its structural formula is following:
2,7,12-three (5-(10-aldehyde radical-anthracene-9-yl) thiophene-2-yl)-5,5 ', 10,10 ', the preparation of 15,15 '-six n-octyls, three polyindenes (CHO3AT3OT), reaction formula is as follows:
Detailed process is following: at N, add POCl among the dinethylformamide solution 100mL
315mmol, nitrogen protection, 0 ℃ is reacted 0.5h down, adds with methylene dichloride dissolved 2,7 12-three (5-(anthracene-9-yl) thiophene-2-yl)-5; 5 ', 10,10 ', 15,15 '-six n-octyls, three polyindene 1.5mmol; In 75-80 ℃ of refluxed reaction 12h, pour reacted mixed solution in frozen water hydrolysis, use dichloromethane extraction, drying is revolved steaming except that desolvating and is obtained crude product; Separate to purify through silica gel column chromatography, eluent is V (sherwood oil): V (methylene dichloride)=2: 1, finally obtains red solid 2,7,12-three (5-(10-aldehyde radical-anthracene-9-yl) thiophene-2-yl)-5; 5 ', 10,10 ', 15,15 '-six n-octyls, three polyindenes.Productive rate: 45%.
Test result is: MALDI/TOF-MS:m/z 1368 (M
+).
The above is merely preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of within spirit of the present invention and principle, being done, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. organic semiconductor material that contains anthracene, thiophene, three polyindenes, it is the compound of any one expression among the following structural formula I-III:
In the formula, A
1, A
2, A
3Be functional group identical or inequality, be selected from H or the electron-withdrawing group any one, R is C
1-C
12Alkyl.
2. the organic semiconductor material that contains anthracene, thiophene, three polyindenes as claimed in claim 1 is characterized in that, said electron-withdrawing group is at least a in fluorine atom, cyanic acid, aldehyde radical, nitro and the carboxyl.
3. the organic semiconductor material that contains anthracene, thiophene, three polyindenes as claimed in claim 1 is characterized in that said A
1, A
2And A
3In have one at least for electron-withdrawing group.
4. the organic semiconductor material that contains anthracene, thiophene, three polyindenes as claimed in claim 1 is characterized in that said R is C
2-C
8Alkyl.
5. preparation method who contains the organic semiconductor material of anthracene, thiophene, three polyindenes, it comprises the steps:
Choose compd A, B, C, D that following structural formula is represented,
Wherein, X is I or Br, and R is C
1-C
12Alkyl;
Under the condition of atmosphere of inert gases and organo-metallic catalyst, compd A or B or C are carried out the Suzuiki reaction with D respectively, generate compound I, compound I I or compound III, wherein A
1, A
2And A
3Be H, its structural formula is as follows:
Under the atmosphere of inert gases protective condition, with A
1, A
2And A
3For compound I, compound I I or the compound III of H are carried out substitution reaction with the compound that electron-withdrawing group is provided respectively in organic solvent system, generate A
1, A
2Or A
3Compound I, compound I I or compound III for electron-withdrawing group.
6. the preparation method who contains the organic semiconductor material of anthracene, thiophene, three polyindenes as claimed in claim 5 is characterized in that said organo-metallic catalyst is the organic palladium metal catalyst system.
7. the preparation method who contains the organic semiconductor material of anthracene, thiophene, three polyindenes as claimed in claim 6 is characterized in that, the temperature of said Suzuiki reaction is 60 ℃～130 ℃.
8. the preparation method who contains the organic semiconductor material of anthracene, thiophene, three polyindenes as claimed in claim 6 is characterized in that, said organic solvent is at least a in THF, glycol dimethyl ether, benzene, chlorobenzene and the toluene.
9. the preparation method who contains the organic semiconductor material of anthracene, thiophene, three polyindenes as claimed in claim 5; It is characterized in that the electron-withdrawing group of said compound I, compound I I or compound III is at least a in fluorine atom, cyanic acid, aldehyde radical, nitro and the carboxyl.
10. like each described organic semiconductor material application in organic photoelectrical material, organic solar batteries device, organic field effect tube device, organic electroluminescence device, organic light storage device or organic laser apparatus that contains anthracene, thiophene, three polyindenes of claim 1-4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010547791.1A CN102464650B (en) | 2010-11-17 | 2010-11-17 | Organic semiconductor material containing anthracene, thiofuran and truxene and preparation method and application of organic semiconductor material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010547791.1A CN102464650B (en) | 2010-11-17 | 2010-11-17 | Organic semiconductor material containing anthracene, thiofuran and truxene and preparation method and application of organic semiconductor material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102464650A true CN102464650A (en) | 2012-05-23 |
| CN102464650B CN102464650B (en) | 2013-10-09 |
Family
ID=46068811
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010547791.1A Expired - Fee Related CN102464650B (en) | 2010-11-17 | 2010-11-17 | Organic semiconductor material containing anthracene, thiofuran and truxene and preparation method and application of organic semiconductor material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102464650B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103923637A (en) * | 2014-04-15 | 2014-07-16 | 西安交通大学 | Truxene-based star-shaped symmetric organic electroluminescence material and preparation method thereof |
| JP2014224047A (en) * | 2013-04-16 | 2014-12-04 | 出光興産株式会社 | Anthracene derivative and organic electroluminescent element prepared using the same |
| CN105906467A (en) * | 2016-04-27 | 2016-08-31 | 厦门大学 | Synthetic method of organic photoelectric material isotruxene |
| CN106883387A (en) * | 2017-02-28 | 2017-06-23 | 华南理工大学 | Based on heteroaromatic and 2,8 S, the conjugated polymer of S dioxydibenze bithiophene units and preparation method and application |
| CN107353891A (en) * | 2017-06-15 | 2017-11-17 | 华南理工大学 | It is a kind of using three indenes fluorenes units as star-like bipolarity small molecule emitter material of core and preparation method and application |
| CN110372585A (en) * | 2019-07-29 | 2019-10-25 | 云谷（固安）科技有限公司 | Compound, organic electroluminescence device and display panel |
-
2010
- 2010-11-17 CN CN201010547791.1A patent/CN102464650B/en not_active Expired - Fee Related
Non-Patent Citations (5)
| Title |
|---|
| 《J. AM. CHEM. SOC.》 20030920 Xiao-Yu Cao et al. Extended pi-Conjugated Dendrimers Based on Truxene 12430-12431 1-10 第125卷, * |
| JIN-LIANG WANG ET AL.: "Shape-Persistent, Truxene-Based, Nano-Sized Bisterpyridine Ruthenium(II) Complexes:Synthesis and Photophysical Properties", 《MACROMOL. RAPID COMMUN.》 * |
| XIAO-YU CAO ET AL.: "Extended π-Conjugated Dendrimers Based on Truxene", 《J. AM. CHEM. SOC.》 * |
| ZHUN MA ET AL.: "Syntheses, characterization, and energy transfer properties of benzothiadiazole-based hyperbranched polyfluorenes", 《POLYMER》 * |
| 陈润锋等: "高分子电致发光材料结构设计方法概述", 《化学进展》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014224047A (en) * | 2013-04-16 | 2014-12-04 | 出光興産株式会社 | Anthracene derivative and organic electroluminescent element prepared using the same |
| CN103923637A (en) * | 2014-04-15 | 2014-07-16 | 西安交通大学 | Truxene-based star-shaped symmetric organic electroluminescence material and preparation method thereof |
| CN105906467A (en) * | 2016-04-27 | 2016-08-31 | 厦门大学 | Synthetic method of organic photoelectric material isotruxene |
| CN106883387A (en) * | 2017-02-28 | 2017-06-23 | 华南理工大学 | Based on heteroaromatic and 2,8 S, the conjugated polymer of S dioxydibenze bithiophene units and preparation method and application |
| CN107353891A (en) * | 2017-06-15 | 2017-11-17 | 华南理工大学 | It is a kind of using three indenes fluorenes units as star-like bipolarity small molecule emitter material of core and preparation method and application |
| CN110372585A (en) * | 2019-07-29 | 2019-10-25 | 云谷（固安）科技有限公司 | Compound, organic electroluminescence device and display panel |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102464650B (en) | 2013-10-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102464650B (en) | Organic semiconductor material containing anthracene, thiofuran and truxene and preparation method and application of organic semiconductor material | |
| CN103951621B (en) | A kind of blue Organic Light Emitting Diode material | |
| CN102899027B (en) | Boron-containing luminescent material and its preparation method and application | |
| CN105384613B (en) | A kind of new electroluminescent organic material and its preparation method and application | |
| CN108658940A (en) | Thermal activation delayed fluorescence material, its synthetic method and OLED luminescent devices | |
| CN106187963A (en) | One is containing anthracene compounds and preparation method thereof and a kind of organic luminescent device | |
| CN108530454A (en) | A kind of fused-polycyclic compounds and its preparation method and application | |
| CN101407717A (en) | High efficient green electroluminescent material for processing solution in diazosulfide luminescent centre | |
| CN106543123A (en) | A kind of connection anthracene compound and preparation method thereof and organic luminescent device | |
| CN104447505B (en) | Stable organic light emitting diode | |
| CN101591531B (en) | Efficient red light electroluminescence material processed by solution using naphthothiadiazole as luminous center | |
| Dang et al. | Manipulating the Molecular Backbone to Achieve Highly Emissive Sky‐Blue AIEgens and Their Applications in Nondoped Organic Light‐Emitting Diodes | |
| CN106397406B (en) | A kind of heteroaromatic derivative and preparation method thereof and a kind of organic electroluminescence device | |
| CN102557857B (en) | Organic semiconductor material, and preparation method and application of organic semiconductor material | |
| CN113416175A (en) | Compound with anthracene benzofuran as core skeleton and application thereof | |
| CN102807554B (en) | Organic semiconductor material containing naphthalene, anthracene and dibenzothiophene sulfone unit, preparation method and application thereof | |
| CN105198875B (en) | A kind of new aromatic amine compound and its preparation and application | |
| CN108516960A (en) | A kind of glyoxaline compound and its organic luminescent device | |
| CN108218891A (en) | A kind of electroluminescent compounds and its preparation method and application | |
| CN102676155B (en) | Material containing anthracene, diazosulfide and trimer indene and preparing method and application therefore | |
| CN110078681A (en) | Luminous organic material and preparation method thereof, organic luminescent device | |
| CN102838585B (en) | Organic semiconductor material containing dibenzothiophene sulfone, and preparation method and application thereof | |
| CN102850320B (en) | Compound containing dibenzothiophene sulfone and preparation method and application thereof | |
| CN102807534B (en) | Organic semiconductor material and preparation method thereof | |
| CN102558168B (en) | Organic semiconductor material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131009 Termination date: 20191117 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |