CN102464650B - 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 PDF

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CN102464650B
CN102464650B CN201010547791.1A CN201010547791A CN102464650B CN 102464650 B CN102464650 B CN 102464650B CN 201010547791 A CN201010547791 A CN 201010547791A CN 102464650 B CN102464650 B CN 102464650B
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anthracene
polyindenes
thiophene
semiconductor material
compound
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CN102464650A (en
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周明杰
王平
梁禄生
张振华
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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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
    • H10K85/615—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
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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

Contain organic semiconductor material of anthracene, thiophene, three polyindenes and its preparation method and application
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 and its preparation method and application.
Background technology
Along with the development of information age, have organic electroluminescent flat-panel monitor (Organic Light Emitting Diodes OLEDs) and big area white-light illuminating efficient, energy-conservation, lightweight and more and more be subjected to 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 by 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 the device instability.Because the energy height of blue light, the energy 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 the 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 and its preparation method and application, be intended to solve in the prior art energy height of blue light in the organic electro-optic device, the energy gap length, efficient is low and stability is not good enough, 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, described preparation method comprises the steps:
Choose compd A, B, C and D that following structural formula is represented,
Figure BDA0000032733410000022
Figure BDA0000032733410000031
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:
Figure BDA0000032733410000032
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, introduces thiophene three polyindenes at anthracene, improves the stability of luminescent material.Thiophene is five member ring heterocyclic compound, at ring 6 πDian Zis is arranged, and meets Huckel's rule, has aromaticity, and environmental stability is good; The cloud density height of thiophene has good optical, electrical properties simultaneously, and its big electron density reduces its HOMO highest occupied molecular orbital (HOMO) energy level, is conducive to hole transport, can produce indigo plant-green glow.Three polyindenes are the highly condensed-nuclei aromaticss of symmetry, have rigid structure.Three polyindenes are carried out suitable chemically modified, and construct novel organic conjugate functional materials as structural motif, will produce unique optics and photoelectronics behavior.In addition, the organic semiconductor material that contains anthracene, thiophene, three polyindenes is introduced electron-withdrawing group, be conducive to make the luminescent spectrum blue shift, the introducing of electron-withdrawing group simultaneously makes the transmission performance of electronics be improved, the balance that is conducive to 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 preparation method's who contains anthracene, thiophene, three polyindenes of the embodiment of the invention 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 purpose of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explaining the present invention, and be not used in restriction 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 as described below:
Figure BDA0000032733410000051
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, cyano group, aldehyde radical, nitro and the carboxyl.Because the introducing of electron-withdrawing group makes the transmission performance of electronics be improved, and is conducive to 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 compound that said structure formula I-III represents, comprise anthracene, thiophene and three polyindenes.Wherein, introduce big substituting group on the anthracene, improve the stability of luminescent material.Thiophene is five member ring heterocyclic compound, at ring 6 πDian Zis is arranged, and meets Huckel's rule, has aromaticity, and environmental stability is good; The cloud density height of thiophene has good optical, electrical properties simultaneously, and its big electron density reduces its HOMO orbital energy level, is conducive to hole transport, can produce indigo plant-green glow.Three polyindenes are the highly condensed-nuclei aromaticss of symmetry, 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 as structural motif, will produce unique optics and photoelectronics behavior.In addition, the organic semiconductor material that contains anthracene, thiophene, three polyindenes is introduced electron-withdrawing group, is conducive to make the luminescent spectrum blue shift, and the introducing of electron-withdrawing group simultaneously makes the transmission performance of electronics be improved, and is conducive to the balance of electric charge.R is selected from C 1-C 12Alkyl, by introducing alkyl chain to improve the solubility property of material, be conducive to film forming processing, 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
Figure BDA0000032733410000061
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 the market or prepare by existing synthetic 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 the functional group of replacement 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 is conducive to 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 as follows: the 1-indone is joined in the mixing solutions of acetic acid 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 as follows:
Figure BDA0000032733410000081
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 tetrahydrofuran (THF) be cooled to-78 ℃ under anaerobic state, 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 ℃ again, 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 the rotary evaporation desolventizing obtains crude product, separates through silica gel column chromatography and purifies, and gets alkyl three polyindenes.Its reaction scheme is as follows:
Figure BDA0000032733410000082
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 as follows:
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, 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 dilute hydrochloric acid, and the bottom organic liquor is reclaimed in extraction, and drying obtains crude product after the rotary evaporation desolventizing, separated through silica gel column chromatography and purified, and recrystallization in the mixed solvent of normal hexane and methylene dichloride obtains compd B.Its reaction scheme is as follows:
Figure BDA0000032733410000092
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.
The 3rd step, alkyl three polyindenes are dissolved in the methylene dichloride, simultaneously with halogen simple substance, as 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 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 obtains crude product after revolving the steaming desolventizing, at ethyl alcohol recrystallization, obtains the yellow crystals product.Its reaction scheme is as follows:
Figure BDA0000032733410000101
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, 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, and drying obtains crude product after the rotary evaporation desolventizing, separate purification through silica gel column chromatography, obtain white solid 9-(thiophene-2-yl) anthracene at last.Its reaction scheme is as follows:
Figure BDA0000032733410000102
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, lucifuge reaction 12h.After reaction finished, mixed solution washed with dilute hydrochloric acid, extract the bottom organic liquor, drying is revolved and is obtained crude product after steaming desolventizing, recrystallization in the mixed solvent of normal hexane/methylene dichloride obtains yellow solid 9-(5-bromothiophene-2-yl)-anthracene.
Figure BDA0000032733410000111
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, inject anhydrous tetrahydro furan under the nitrogen protection, system is cooled to-78 ℃ with dry ice/acetone batch; slowly be added dropwise to the hexane solution of n-Butyl Lithium; solid dissolves fully, stirs this mixture 1h under same temperature, drips trimethyl borate rapidly in reaction mixture; temperature of reaction slowly is increased to room temperature, stirs this reaction mixture 12h.When reaction is finished, 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 and is obtained crude product after steaming desolventizing.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:
Figure BDA0000032733410000112
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; inject anhydrous tetrahydro furan under the nitrogen protection; system is cooled to-78 ℃ with dry ice/acetone batch; slowly be added dropwise to the hexane solution of n-Butyl Lithium, solid dissolves fully, stirs this mixture 1.5h under same temperature; in reaction mixture, add 2-isopropoxy-4 rapidly; 4,5,5-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 finished, add the saturated NaCl aqueous solution therein, chloroform extraction, anhydrous sodium sulfate drying filters, and revolves to obtain crude product after steaming desolventizing.Separate purification through silica gel column chromatography, its reaction formula is as follows:
Figure BDA0000032733410000121
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 tetrahydrofuran (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:
Figure BDA0000032733410000122
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 the compound I, compound I I and the compound III that replace.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 number of electron-withdrawing group replacement can be by different feed ratio controls.Its reaction formula is as follows:
Figure BDA0000032733410000131
In aforesaid method, the synthetic route of compd A, B, C, D monomer is fairly simple and ripe, thereby reduces technical process, reduces manufacturing cost.And the Suzuki coupling reaction is a kind of very ripe organometallic coupling reaction, and productive rate height, mild condition are easy to control.
The organic semiconductor material that contains anthracene, thiophene, three polyindenes that scans present embodiment by differential thermal analysis 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 as organic light storage device, organic non-linear optical properties and organic laser apparatus and following similar all are with the organic semiconductor material that contains anthracene, thiophene, three polyindenes of present embodiment optical memory material, nonlinear material, laserable material or the 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 above-described embodiment, it comprises glass-base 31, anode 32, hole transmission layer 33, luminescent layer 34, hole blocking layer 35, electron transfer layer 36, buffer layer 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 above-described embodiment; Hole blocking layer 35 can be 2,9-dimethyl-4,7-phenylbenzene-9,10-phenanthroline (BCP); Electron transfer layer 36 can be oxine aluminium; Buffer layer 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 organic semiconductor material that contains anthracene, thiophene, three polyindenes that electrophilic replaces, have the performance of hole and electric transmission concurrently, the son transmission that is conducive to dam, 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, be conducive to flat-panel monitor and the illuminating device of superior performance of future generation.
Below by 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 the market in other embodiments, are not limited to this.
Embodiment one:
The organic compound 2-that contains anthracene, thiophene, three polyindene unit of present embodiment (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 as follows:
Figure BDA0000032733410000151
The preparation process of above-mentioned AT1ET organic semiconductor material is as follows:
The preparation of step 1, three polyindenes, reaction formula is as follows:
Concrete preparation process is as follows: 1-indone 10mmol is joined in the mixing solutions that contains acetic acid 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 as follows: three polyindene 8mmol are added in the reaction flask; vacuumize, after the logical nitrogen circulation 3 times; make reaction system be in anaerobic state; inject anhydrous tetrahydro furan 50mL under the nitrogen protection, system is cooled to-78 ℃ with dry ice/acetone batch, slowly be 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 ℃ again, 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 the steaming desolventizing, obtain crude product, separate through silica gel column chromatography and purify, eluent is 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:
Figure BDA0000032733410000161
Detailed process is as follows: 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:
Figure BDA0000032733410000162
Detailed process is as follows: 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, adding is dissolved with the anhydrous tetrahydrofuran solution 50mL of 2-thienyl boric acid 5.5mmol, the Na of tetra-triphenylphosphine palladium 0.01mmol, 2mol/L under the nitrogen protection 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, ethyl acetate extraction three times, organic phase is washed with sodium chloride aqueous solution, drying obtains crude product after the rotary evaporation desolventizing, separates through silica gel column chromatography and purifies, 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:
Figure BDA0000032733410000171
Detailed process is as follows: 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, lucifuge reaction 12h.After reaction finished, mixed solution washed with dilute hydrochloric acid, extract the bottom organic liquor, drying is revolved and is obtained crude product after steaming desolventizing, 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:
Figure BDA0000032733410000172
Detailed process is as follows: 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; inject anhydrous tetrahydro furan (50mL) under the nitrogen protection; 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, 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 finished, 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 and is obtained crude product after steaming desolventizing.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:
Figure BDA0000032733410000181
Detailed process is as follows: 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, adding is dissolved with 5-(anthracene-9-yl) thiophene-anhydrous tetrahydrofuran solution 50mL of 2-ylboronic acid 3.1mmol, Na of tetra-triphenylphosphine palladium 0.01mmol, 2mol/L under the nitrogen protection 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, and drying is revolved and obtained crude product after steaming desolventizing, separate purification through silica gel column chromatography, eluent is V (sherwood oil): V (methylene dichloride)=12: 1, obtains 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:
The organic compound 2 that contains anthracene, thiophene, three polyindene unit of present embodiment, 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 as follows:
Figure BDA0000032733410000182
The preparation process of above-mentioned AT2ET organic semiconductor material is as follows:
Step 1,2,7-two bromo-5,5 ', 10,10 ', 15,15 '-preparation of Hexaethyl three polyindenes, reaction formula is as follows:
Figure BDA0000032733410000191
Detailed process is as follows: with 5,5 ', 10,10 ', 15,15 '-Hexaethyl three polyindene 5mmol are dissolved in the 25mL methylene dichloride, simultaneously NBS 10.5mmol is dissolved in the 10mL methylene dichloride, under 0 ℃ of condition, the dichloromethane solution of NBS slowly splashed into contain 5,5 ', 10,10 ', 15,15 '-reaction vessel of Hexaethyl three polyindenes in, splash into the 1ml Glacial acetic acid, lucifuge reaction 12h.After reaction finished, mixed solution washed with dilute hydrochloric acid, extract the bottom organic liquor, drying is revolved and is obtained crude product after steaming desolventizing, separates through silica gel column chromatography and purifies, recrystallization in the mixed solvent of normal hexane and methylene dichloride, obtain 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:
Figure BDA0000032733410000192
Detailed process is as follows: with 2; 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, add under the nitrogen protection and be dissolved with 5-(anthracene-9-yl) thiophene-anhydrous tetrahydrofuran solution 50mL of 2-ylboronic acid 8.2mmol, Na of 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, and uses ethyl acetate extraction three times, organic phase is washed with sodium chloride aqueous solution, and drying is revolved the steaming desolventizing, obtain crude product, separate to purify through silica gel column chromatography, eluent is V (sherwood oil): V (methylene dichloride)=10: 1, obtain 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:
The organic compound 2,7 that contains anthracene, thiophene, three polyindene unit of present embodiment, 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 as follows:
Figure BDA0000032733410000201
The preparation process of above-mentioned AT3ET organic semiconductor material is as follows:
Step 1,2,7,12-three bromo-5,5 ', 10,10 ', 15,15 '-preparation of Hexaethyl three polyindenes, reaction formula is as follows:
Figure BDA0000032733410000202
Detailed process is as follows: with 5,5 ', 10,10 ', 15,15 '-Hexaethyl three polyindene 5mmol are dissolved in the 25mL methylene dichloride, simultaneously bromine 1mL is dissolved in the 10mL methylene dichloride, under 0 ℃ of condition, the dichloromethane solution of bromine slowly splashed into contain 5,5 ', 10,10 ', 15,15 '-reaction system of Hexaethyl three polyindenes in, after 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 the steaming desolventizing, 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:
Figure BDA0000032733410000211
Detailed process is as follows: with 2; 7; 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, adding is dissolved with 5-(anthracene-9-yl) thiophene-anhydrous tetrahydrofuran solution 50mL of 2-ylboronic acid 11mmol, Na of tetra-triphenylphosphine palladium 0.01mmol, 2mol/L under the nitrogen protection 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, and drying is revolved and obtained crude product after steaming desolventizing, separate to purify through silica gel column chromatography, eluent is V (sherwood oil): V (methylene dichloride)=8: 1, obtains yellow solid 2 at last, 7,12-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:
The organic compound 2,7 that contains anthracene, thiophene, three polyindene unit of present embodiment, 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 as follows:
Figure BDA0000032733410000221
The preparation process of above-mentioned AT3HT organic semiconductor material is as follows:
Step 1,5,5 ', 10,10 ', the preparation of 15,15 '-six n-hexyls, three polyindenes, reaction formula is as follows:
Detailed process is as follows: three polyindene 8mmol are added in the reaction flask; vacuumize, after the logical nitrogen circulation 3 times; make reaction system be in anaerobic state; inject anhydrous tetrahydro furan 50mL under the nitrogen protection, system is cooled to-78 ℃ with dry ice/acetone batch, slowly be 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 ℃ again, 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 the steaming desolventizing, obtain crude product, separate to purify through silica gel column chromatography, eluent is 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:
Figure BDA0000032733410000231
Detailed process is as follows: with 5,5 ', 10,10 ', 15,15 '-six n-hexyls, three polyindene 5mmol are dissolved in the 25mL methylene dichloride, simultaneously bromine 1mL is dissolved in the 10mL methylene dichloride, under 0 ℃ of condition, the dichloromethane solution of bromine slowly splashed into contain 5,5 ', 10,10 ', 15, in the reaction system of 15 '-six n-hexyls, three polyindenes, after 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 obtains crude product, recrystallization in ethanol after revolving the steaming desolventizing, 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:
Figure BDA0000032733410000232
Detailed process is as follows: vacuumize, after the logical nitrogen circulation 3 times; make reaction system be in anaerobic state; in reaction flask, add 9-(5-bromothiophene-2-yl)-anthracene 7mmol under the nitrogen protection; inject 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, stirs this mixture 1.5h under same temperature.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.After reaction finishes, add the saturated NaCl aqueous solution, chloroform extraction, anhydrous sodium sulfate drying filters, and revolves to obtain crude product after steaming desolventizing.Separate to purify through silica gel column chromatography, eluent is V (sherwood oil): V (ethyl 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:
Figure BDA0000032733410000241
Detailed process is as follows: with 2,7,12-, 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, adding is dissolved with 2-(4,4 under the nitrogen protection; 5; 5-tetramethyl--1,3,2-two assorted oxygen pentaboranes)-5-(anthracene-9-yl) the anhydrous tetrahydrofuran solution 60mL of thiophene 9.5mmol, the Na of 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 ethyl acetate extraction three times after finishing, organic phase is washed with sodium chloride aqueous solution, and drying is revolved and obtained crude product after steaming desolventizing, separate to purify through silica gel column chromatography, eluent is V (sherwood oil): V (methylene dichloride)=9: 1, obtains yellow solid 2 at last, 7,12-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:
The organic compound 2,7 that contains anthracene, thiophene, three polyindene unit of present embodiment, 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 as follows:
Figure BDA0000032733410000251
The preparation process of above-mentioned AT3OT organic semiconductor material is as follows:
Step 1,5,5 ', 10,10 ', the preparation of 15,15 '-six n-octyls, three polyindenes, reaction formula is as follows:
Figure BDA0000032733410000252
Detailed process is as follows: three polyindene 8mmol are added in the reaction flask; vacuumize, after the logical nitrogen circulation 3 times; make reaction system be in anaerobic state; inject anhydrous tetrahydro furan 50mL under the nitrogen protection, system is cooled to-78 ℃ with dry ice/acetone batch, slowly be 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 ℃ again, 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 the steaming desolventizing, obtain crude product, separate to purify through silica gel column chromatography, eluent is 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:
Figure BDA0000032733410000261
Detailed process is as follows: with 5,5 ', 10,10 ', 15,15 '-six n-octyls, three polyindene 5mmol are dissolved in the 25mL methylene dichloride, simultaneously bromine 1mL is dissolved in the 10mL methylene dichloride, under 0 ℃ of condition, the dichloromethane solution of bromine slowly splashed into contain 5,5 ', 10,10 ', 15, in the reaction system of 15 '-six n-octyls, three polyindenes, after 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 obtains crude product, recrystallization in ethanol after revolving the steaming desolventizing, 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 as follows: with 2; 7,12-, 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, adding is dissolved with 5-(anthracene-9-yl) thiophene-anhydrous tetrahydrofuran solution 50mL of 2-ylboronic acid 10mmol, Na2CO3 aqueous solution 34ml of tetra-triphenylphosphine palladium 0.01mmol, 2mol/L under the nitrogen protection, 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 ethyl acetate extraction three times after finishing, organic phase is washed with sodium chloride aqueous solution, and drying is revolved and obtained crude product after steaming desolventizing, separate to purify through silica gel column chromatography, eluent is V (sherwood oil): V (methylene dichloride)=10: 1, obtains yellow solid 2 at last, 7,12-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:
The organic compound 2-that contains anthracene, thiophene, three polyindene unit of present embodiment (5-(10-cyano group-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 as follows:
Figure BDA0000032733410000271
2-(5-(10-cyano group-anthracene-9-yl) thiophene-2-yl)-5,5 ', 10,10 ', 15,15 '-preparation of Hexaethyl three polyindenes (CNAT3ET), reaction formula is as follows:
Figure BDA0000032733410000272
Detailed process is as follows: at N, add 2,7,12-three (5-(anthracene-9-yl) thiophene-2-yl)-5 among the dinethylformamide solution 30mL; 5 ', 10,10 '; 15,15 '-Hexaethyl three polyindene 1.5mmol and cuprous cyanide 3mmol, back flow reaction 20h under nitrogen protection.Be cooled to 80 ℃ subsequently, in system, add the mixing solutions of iron(ic) chloride 3mmol, concentrated hydrochloric acid 5mL and water 5mL, stir under the room temperature behind the reaction 1h and spend the night.Reaction is poured in the beaker that fills big water gaging after finishing, and filters brown precipitate, water and washing with alcohol.Water layer is dry after with dichloromethane extraction, revolve steaming, two portions solid is merged through silica gel column chromatography separation purification, eluent is V (sherwood oil): V (methylene dichloride)=6: 1, the final light red solid 2-(5-(10-cyano group-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:
The organic compound 2,7 that contains anthracene, thiophene, three polyindene unit of present embodiment, 12-three (5-(10-cyano group-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 as follows:
Figure BDA0000032733410000281
2,7,12-three (5-(10-cyano group-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 as follows: at N, add 2,7,12-three (5-(anthracene-9-yl) thiophene-2-yl)-5 among the dinethylformamide solution 30mL; 5 ', 10,10 '; 15,15 '-Hexaethyl three polyindene 1.5mmol and cuprous cyanide 15mmol, back flow reaction 20h under nitrogen protection.Be cooled to 80 ℃ subsequently, in system, add the mixing solutions of iron(ic) chloride 15mmol, concentrated hydrochloric acid 15mL and water 15mL, stir under the room temperature behind the reaction 1h and spend the night.Reaction is poured in the beaker that fills big water gaging after finishing, and filters brown precipitate, water and washing with alcohol.Water layer is dry after with dichloromethane extraction, revolve steaming, two portions solid is merged through silica gel column chromatography separation purification, eluent is V (sherwood oil): V (methylene dichloride)=3: 1, finally obtains garnet solid 2,7,12-three (5-(10-cyano group-anthracene-9-yl) thiophene-2-yl)-5,5 ', 10,10 ', 15,15 '-Hexaethyl three polyindenes.Productive rate: 51%.The electroluminescent spectrum figure of product as shown in Figure 4, 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:
The organic compound 2,7 that contains anthracene, thiophene, three polyindene unit of present embodiment, 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 as follows:
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 as follows: at N, add POCl among the dinethylformamide solution 100mL 315mmol, nitrogen protection, 0 ℃ is reacted 0.5h down; adding is with 2,7 of methylene dichloride dissolving, 12-three (5-(anthracene-9-yl) thiophene-2-yl)-5; 5 ', 10,10 '; 15,15 '-Hexaethyl three polyindene 1.5mmol, in 75-80 ℃ of following back flow reaction 12h; pour reacted mixed solution in frozen water hydrolysis, use dichloromethane extraction, drying; revolve and steam desolventizing and obtain crude product, separate through silica gel column chromatography and purify, eluent is V (sherwood oil): V (methylene dichloride)=1: 1; the final red solid 2 that obtains; 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:
The organic compound 2,7 that contains anthracene, thiophene, three polyindene unit of present embodiment, 12-three (5-(10-cyano group-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 as follows:
2,7,12-three (5-(10-cyano group-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 as follows: at N, add 2,7,12-three (5-(anthracene-9-yl) thiophene-2-yl)-5 among the dinethylformamide solution 30mL; 5 ', 10,10 '; 15,15 '-six n-hexyls, three polyindene 1.5mmol and cuprous cyanide 15mmol, back flow reaction 20h under nitrogen protection.Be cooled to 80 ℃ subsequently, in system, add the mixing solutions of iron(ic) chloride 15mmol, concentrated hydrochloric acid 15mL and water 15mL, stir under the room temperature behind the reaction 1h and spend the night.Reaction is poured in the beaker that fills big water gaging after finishing, and filters brown precipitate, water and washing with alcohol.Water layer is dry after with dichloromethane extraction, revolve steaming, two portions solid is merged through silica gel column chromatography separation purification, eluent is V (sherwood oil): V (methylene dichloride)=4: 1, finally obtains garnet solid 2,7,12-three (5-(10-cyano group-anthracene-9-yl) thiophene-2-yl)-5,5 ', 10,10 ', 15,15 '-six n-hexyls, three polyindenes.Productive rate: 53%.
Test result is: MALDI/TOF-MS:m/z 1696 (M +).
Embodiment ten:
The organic compound 2,7 that contains anthracene, thiophene, three polyindene unit of present embodiment, 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 as follows:
Figure BDA0000032733410000311
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:
Figure BDA0000032733410000312
Detailed process is as follows: at N, add POCl among the dinethylformamide solution 100mL 315mmol, nitrogen protection, 0 ℃ is reacted 0.5h down; adding is with 2,7 of methylene dichloride dissolving, 12-three (5-(anthracene-9-yl) thiophene-2-yl)-5; 5 ', 10,10 '; 15,15 '-six n-octyls, three polyindene 1.5mmol are in 75-80 ℃ of following back flow reaction 12h; pour reacted mixed solution in frozen water hydrolysis, use dichloromethane extraction, drying; revolve and steam desolventizing and obtain crude product, separate through silica gel column chromatography and purify, eluent is V (sherwood oil): V (methylene dichloride)=2: 1; the final red solid 2 that obtains; 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 only is preferred embodiment of the present invention, not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.

Claims (9)

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:
Figure FDA00003157992400011
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; Described electron-withdrawing group is at least a in fluorine atom, cyano group, aldehyde radical, nitro and the carboxyl.
2. the organic semiconductor material that contains anthracene, thiophene, three polyindenes as claimed in claim 1 is characterized in that described A 1, A 2And A 3In have one at least for electron-withdrawing group.
3. the organic semiconductor material that contains anthracene, thiophene, three polyindenes as claimed in claim 1 is characterized in that, described R is C 2-C 8Alkyl.
4. 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,
A：
Figure FDA00003157992400021
B： C：
D:
Figure FDA00003157992400024
Or
Figure FDA00003157992400025
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 Suzuki 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:
Figure FDA00003157992400026
Figure FDA00003157992400031
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; Described electron-withdrawing group is at least a in fluorine atom, cyano group, aldehyde radical, nitro and the carboxyl.
5. the preparation method who contains the organic semiconductor material of anthracene, thiophene, three polyindenes as claimed in claim 4 is characterized in that, described organo-metallic catalyst is the organic palladium metal catalyst system.
6. the preparation method who contains the organic semiconductor material of anthracene, thiophene, three polyindenes as claimed in claim 5 is characterized in that, the temperature of described Suzuki reaction is 60 ° of C～130 ° C.
7. the preparation method who contains the organic semiconductor material of anthracene, thiophene, three polyindenes as claimed in claim 5 is characterized in that, described organic solvent is at least a in tetrahydrofuran (THF), glycol dimethyl ether, benzene, chlorobenzene and the toluene.
8. the preparation method who contains the organic semiconductor material of anthracene, thiophene, three polyindenes as claimed in claim 4, it is characterized in that the electron-withdrawing group of described compound I, compound I I or compound III is at least a in fluorine atom, cyano group, aldehyde radical, nitro and the carboxyl.
9. as 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 1-3.
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