CN106188090A - A kind of stereochemical structure organic semiconducting materials and method for preparing monomer - Google Patents

A kind of stereochemical structure organic semiconducting materials and method for preparing monomer Download PDF

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CN106188090A
CN106188090A CN201610522100.XA CN201610522100A CN106188090A CN 106188090 A CN106188090 A CN 106188090A CN 201610522100 A CN201610522100 A CN 201610522100A CN 106188090 A CN106188090 A CN 106188090A
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semiconducting materials
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stereochemical structure
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孟鸿
史晶晶
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Peking University Shenzhen Graduate School
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
    • C07D495/14—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/08—Hydrogen atoms or radicals containing only hydrogen and carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds

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Abstract

The open a kind of stereochemical structure organic semiconducting materials of the present invention and method for preparing monomer.Stereochemical structure organic semiconducting materials monomer whose structural formula is as follows: The method preparation of the present invention is simple, and obtain the monomeric compound of buttferfly-type, and monomeric compound has four different polymerization site, it is obtained in that the compound that different loci is polymerized when making to be polymerized at different conditions, thus obtains the polymer organic semiconductor material of different types of solid type.The present invention adds the derivant of thiophene or EDOT on parent nucleus, have adjusted HOMO and the lumo energy of material further, it is thus achieved that more excellent organic semiconducting materials, and preparation process is simple and convenient, and product cost is greatly reduced, and provides the foundation for application.

Description

A kind of stereochemical structure organic semiconducting materials and method for preparing monomer
Technical field
The present invention relates to optics, electricity field, particularly relate to a kind of stereochemical structure organic semiconducting materials and be prepared by monomer Method.
Background technology
Organic semiconducting materials is a kind of material with semiconductor property, at Organic Light Emitting Diode (OLED), calcium titanium Ore deposit, organic electrochromic (OEC), organic field effect tube (OTFT), organic solar batteries (OPV) have widely should With.
For traditional inorganic semiconductor material, such as silicon, germanium, gallium nitride, GaAs etc. make science and technology enter rapidly Information age, exhibit one's skill to the full in the information age at a high speed.Although, in development in science and technology, inorganic semiconductor material shows a lot Superiority, but, inorganic semiconductor material remains its limitation, and the kind of material is more single, preparation technology Complicated, more high shortcomings of cost greatly limit its development.For overcoming these shortcomings, organic semiconducting materials meets the tendency And give birth to.Organic semiconducting materials has the advantages such as processing is simple, cost is relatively low, and additionally organic semiconducting materials can also pass through Fine setting in structure, obtains different energy level scope, semi-conducting material of different nature.
Organic semiconducting materials structure has carbon-carbon double bond structure, the P of two carbon atomsZTrack define bonding orbital and Antibonding orbital, forms HOMO (highest occupied molecular orbital) and LUMO (minimum occupied orbital), the HOMO in organic semiconductor the most respectively The valence band in inorganic semiconductor and conduction band is equivalent to lumo energy.After electronics is excited on LUMO by HOMO, HOMO lacks Electronically forming hole, LUMO electron rich, the two forms hole-electron pair, and the character of energy level have impact on organic semiconducting materials Various optical and electrical properties.
Organic Light Emitting Diode (OLED) is under the driving of electric field, electronics and hole respectively through respective implanted layer and After transport layer, moving to luminescent layer, and then a class luminescent device of the luminescence that is stimulated.OLED has self-luminous, high brightness, height Contrast, low consumption, flexibility, volume are little etc., and feature demonstrates the potentiality in future display market and huge business valency Value.Organic semiconducting materials is relatively broad as the most basic element purposes of OLED, and it serves not only as emitting layer material, it is also possible to Composition implanted layer and transport layer.As can be seen here, the performance of research semi-conducting material is to improve the key of the various performance of OLED.Exploitation The OLED material with commercialization potential value is our research basis.
OEC (organic electrochromic) is the most alive effect, by dissociating and going dissociation process generation polymer altogether The torsion of yoke chain, causes the optics electrical property fundamental change of polymeric material under different voltage conditions, it is achieved different colours it Between transformation.Compared with inorganic electrochromic material, organic conductive macromolecule polymer seems even better: it can be by right Functional group's fine setting of the monomer of organic conductive macromolecule polymer is modified, it is achieved to the color of material, energy gap, coloration efficiency, change The regulation of color time, stability etc.；It addition, organic conductive macromolecule polymeric material also has low cost and to be prone to processing etc. excellent Point.And limited functional group is modified, make material convert in any condition and there is also technical difficulty.Recent report Showing in conducting polymer that the material of pure color is less, some then by the mixing of material, regulates the color of material.But color Can't be close to pure color.
In organic field effect tube (OTFT), perovskite, organic solar batteries (OPV), organic semiconducting materials Also it is requisite.The organic semiconductor layer of OTFT, as the medium of carrier mobility, affects its mobility, switch The critical natures such as ratio, life-span, voltage；As can be seen here, the organic semiconducting materials of function admirable be improve OLED, perovskite, One of factors of performance most critical such as OEC, OTFT, OPV.But, current organic semiconducting materials is the most also deposited In a lot of problems.
Therefore, prior art has yet to be improved and developed.
Summary of the invention
In view of above-mentioned the deficiencies in the prior art, it is an object of the invention to provide a kind of stereochemical structure organic semiconducting materials And method for preparing monomer, it is intended to regulation HOMO (highest occupied molecular orbital) and LUMO (minimum occupied orbital) energy level and bandgap (band gap), obtains the stereochemical structure organic semiconducting materials of premium properties.
Technical scheme is as follows:
A kind of stereochemical structure organic semiconducting materials, wherein, monomer whose structural formula is as follows:
Wherein, parent nucleus is the pyrroles of substituted base on thiophene, bithiophene, pyrroles, nitrogen, bithiophene, naphthalene, anthracene, three acenes, thiophene Fen acene or BTBT；
R1And R2One in following substituent group: H, methyl, ethyl propyl, isopropyl, direct-connected many carbon alkyl, fork chain are many Carbon alkyl, cyclohexyl, face or or to fluorine cyclohexyl, alkoxyl, phenyl, trifluoromethoxy, trifluoromethylthio, face or or right Fluorine or Trifluoromethoxyphen-l, face or or to fluorine or trifluoromethylthio phenyl.
A kind of preparation method of stereochemical structure organic semiconducting materials monomer as above, wherein, including:
Step A, bromination reaction: female ring compound is dissolved in the mixed solvent of glacial acetic acid and chloroform, dropwise drips under room temperature Add Br2, it is stirred for a period of time, then heated overnight at reflux；After being cooled to room temperature, washing, separate out compound as white solid, then For several times, under room temperature, vacuum drying obtains compound 1a in washing；
Step B, under cryogenic n-BuLi is added containing R1And R2The thiophene of substituent group or EDOT or EDOT derivant THF solvent in, placement is stirred at room temperature；Add ClSn (C4H9)3, react overnight under room temperature condition；Cancellation successively, extract, close And organic facies, organic facies is washed for several times, is dried, and after being spin-dried for, distillation obtains compound 2a；
Step C, Stille react: be mixed to join in THF solvent by compound 1a and compound 2a, be passed through N2After, Add catalyst under room temperature condition, reflux 16～24 hours；It is cooled to room temperature, dilutes successively, wash, merge organic facies and do Dry, add silica gel and be spin-dried for, then eluting, normal-temperature vacuum is dried.
The preparation method of described stereochemical structure organic semiconducting materials monomer, wherein, in described step A, at 75-80 DEG C Under the conditions of heated overnight at reflux.
The preparation method of described stereochemical structure organic semiconducting materials monomer, wherein, in described step B, cryogenic conditions For-78 DEG C.
The preparation method of described stereochemical structure organic semiconducting materials monomer, wherein, in described step B, mixing time It it is 1.5 hours.
The preparation method of described stereochemical structure organic semiconducting materials monomer, wherein, in described step C, at 100 DEG C of bars Reflux under part.
A kind of preparation method of stereochemical structure organic semiconducting materials monomer as above, wherein, including step:
A, bromination reaction: substituted female ring compound is dissolved in dry THF, under cryogenic conditions under the conditions of add NBS, Stir a period of time under room temperature, after being spin-dried for, washing, add dichloromethane extraction, merge organic facies, add anhydrous magnesium sulfate and do Dry, sucking filtration takes filtrate, adds silica gel and is spin-dried for, and crosses post and obtains solid chemical compound 1b；
B, under cryogenic n-BuLi is added containing R1And R2The thiophene of substituent group or EDOT or EDOT derivant In THF solvent, placement is stirred at room temperature；Add ClSn (C4H9)3, react overnight under room temperature condition；Cancellation successively, extract, merge Organic facies, organic facies is washed for several times, is dried, and after being spin-dried for, distillation obtains compound 2b；
C, Stille react: be mixed to join in toluene by compound 1b and compound 2b, be passed through N2After, at room temperature condition Lower addition catalyst, refluxes 16～24 hours；It is cooled to room temperature, dilutes successively, wash, merge organic facies and be dried, add Silica gel is spin-dried for, then eluting, and normal-temperature vacuum is dried.
The preparation method of described stereochemical structure organic semiconducting materials monomer, wherein, in described step A, at 75-80 DEG C Under the conditions of heated overnight at reflux.
The preparation method of described stereochemical structure organic semiconducting materials monomer, wherein, in described step B, cryogenic conditions For-78 DEG C.
The preparation method of described stereochemical structure organic semiconducting materials monomer, wherein, in described step B, mixing time It it is 1.5 hours.
Beneficial effect: the method preparation of the present invention is simple, and obtain the monomeric compound of buttferfly-type, and monomer chemical combination Thing has four different polymerization site so that be obtained in that, during polymerization, the compound that different loci is polymerized at different conditions, Thus obtain the polymer organic semiconductor material of different types of solid type.The present invention adds thiophene or EDOT's on parent nucleus Derivant, have adjusted HOMO and the lumo energy of material, it is thus achieved that more excellent organic semiconducting materials further, and preparation Process is simple and convenient, and product cost is greatly reduced, and provides the foundation for application.
Accompanying drawing explanation
Fig. 1 is the flow chart of stereochemical structure organic semiconductor monomeric compound preparation method of the present invention.
Fig. 2 is the schematic diagram of the embodiment of the present invention 1 neutral body structure organic semiconductor monomeric compound preparation process.
Fig. 3 is conducting polymer thin film structural representation.
Fig. 4 a with 4b is the cyclic voltammetry curve of two kinds of different conducting polymer thin films in the embodiment of the present invention 3.
Detailed description of the invention
The present invention provides a kind of stereochemical structure organic semiconducting materials and method for preparing monomer, for make the purpose of the present invention, Technical scheme and effect are clearer, clear and definite, and the present invention is described in more detail below.Should be appreciated that described herein Specific embodiment only in order to explain the present invention, is not intended to limit the present invention.
A kind of stereochemical structure organic semiconducting materials provided by the present invention, monomer whose structural formula is as follows:
Parent nucleus is the pyrroles of substituted base on thiophene, bithiophene, pyrroles, nitrogen, bithiophene, naphthalene, anthracene, three acenes, thieno Benzene, BTBT；
R1And R2One in following substituent group: H, methyl, ethyl propyl, isopropyl, direct-connected many carbon alkyl, fork chain are many Carbon alkyl, cyclohexyl, face or or to fluorine cyclohexyl, alkoxyl, phenyl, trifluoromethoxy, trifluoromethylthio, face or or right Fluorine or Trifluoromethoxyphen-l, face or or to fluorine or trifluoromethylthio phenyl.
In the present invention, its possible structure of organic semiconducting materials monomer is as follows:
Such as, the present invention provides a kind of three-dimensional organic semiconducting materials based on bithiophene, and monomer whose structural formula is as follows:
Wherein, R1And R2One in following substituent group: H, methyl, ethyl propyl, isopropyl, direct-connected many carbon alkyl, fork Chain many carbon alkyl, cyclohexyl, face or or to fluorine cyclohexyl, alkoxyl, phenyl, trifluoromethoxy, trifluoromethylthio, face or Or to fluorine or Trifluoromethoxyphen-l, face or or to fluorine or trifluoromethylthio phenyl.Described face or to fluorine cyclohexyl Refer to face fluorine cyclohexyl, a fluorine cyclohexyl or to fluorine cyclohexyl.Described face or fluorine or Trifluoromethoxyphen-l are referred to Face fluorine methoxyphenyl, a fluorine methoxyphenyl, to fluorine methoxyphenyl, face Trifluoromethoxyphen-l, a (Trifluoromethoxy)benzene Base, to Trifluoromethoxyphen-l.
Such organic semiconducting materials its be to add containing R (R on the four combinations site of bithiophene1Or R2) substituent group EDOT (3,4-rthylene dioxythiophene), be used for regulate the different optics of semi-conducting material, electrical properties.Owing to material has four Individual different binding site, therefore, uses different methods to be polymerized, and can obtain different loci polymerization has solid type structure spy The organic semiconducting materials of point.
In the present invention, four sites of bithiophene respectively connect one containing R (R1Or R2) EDOT of substituent group, repolymerization obtains Stereochemical structure organic semiconducting materials.Add different substituent groups, make band gap (band gap) size change, absorbing wavelength It is moved, causes a series of performance of material to change.
So, its possible structure is as follows
The present invention also provides for the preparation method of a kind of stereochemical structure organic semiconducting materials monomer as above, its bag Include:
Step S1, bromination reaction: female ring compound is dissolved in the mixed solvent of glacial acetic acid and chloroform, dropwise drips under room temperature Add Br2, it is stirred for a period of time, then heated overnight at reflux；After being cooled to room temperature, washing, separate out compound as white solid, then For several times, under room temperature, vacuum drying obtains compound 1a in washing；
Step S2, under cryogenic n-BuLi is added containing R1And R2The thiophene of substituent group or EDOT or EDOT derive In the THF solvent of thing, placement is stirred at room temperature；Add ClSn (C4H9)3, react overnight under room temperature condition；Cancellation successively, extraction, Merging organic facies, organic facies is washed for several times, is dried, and after being spin-dried for, distillation obtains compound 2a；
Step S3, Stille react: be mixed to join in THF solvent by compound 1a and compound 2a, be passed through N2After, Add catalyst under room temperature condition, reflux 16～24 hours；It is cooled to room temperature, dilutes successively, wash, merge organic facies and do Dry, add silica gel and be spin-dried for, then eluting, normal-temperature vacuum is dried.
Further, in described step S1, heated overnight at reflux under the conditions of 75-80 DEG C.
Further, in described step S2, cryogenic conditions is-78 DEG C.
Further, in described step S2, mixing time is 1.5 hours.
Further, in described step S3, reflux under the conditions of 100 DEG C.
Such as above-mentioned stereochemical structure organic semiconducting materials based on bithiophene, monomer whose preparation method, including such as Lower step:
S1, bromination reaction: bithiophene is dissolved in the mixed solvent of glacial acetic acid and chloroform, dropwise drip Br under room temperature2, then stir Mix a period of time, reheat backflow overnight；After being cooled to room temperature, washing, separate out compound as white solid, then wash for several times, often The lower vacuum drying of temperature obtains compound 1a；
S2, being added by n-BuLi under cryogenic in the THF solvent of EDOT, placement is stirred at room temperature；Add ClSn (C4H9)3, react overnight under room temperature condition；Cancellation successively, extracting, merge organic facies, organic facies is washed for several times, is dried, after being spin-dried for Distillation obtains compound 2a；
S3, Stille react: it is molten that the compound (compound 1a and compound 2a) upper two steps obtained is mixed to join THF In agent, it is passed through N2After, add catalyst at ambient temperature, reflux 16～24 hours；It is cooled to room temperature, dilute successively, wash, Merging organic facies and be dried, adding silica gel and be spin-dried for, then eluting, normal-temperature vacuum is dried to obtain compound 3.
Above-mentioned organic semiconducting materials monomer (compound 3) is designated as t-EDOT-TT by the present invention, is obtained by Gaussian Computation The HOMO energy level of t-EDOT-TT, is a kind of potential OLED hole injection layer material.
Now using as a example by electrochromic material, t-EDOT-TT and obtain polymer as electroluminescent by electropolymerization The performance test methods of off-color material, is first electrochemical deposition, by oxidoreduction by organic semiconductor monomer be polymerized and Deposit to, in ito glass substrate (transparent glass), obtain conducting polymer thin film (i.e. conductive polymer coating), by circulation Voltammetry obtains C-V curve.In ito glass substrate, i.e. plate conductive polymer coating, then under different voltage, realize color Change.
Concrete manufacturing process is as follows, first that ito glass substrate is in succession each ultrasonic in abluent, acetone, isopropanol Ripple cleans 30 minutes, then through ethanol purge, drying for standby；Preparation electrolyte concentration is the TBAPF of 0.1M6Saturated monomer molten Liquid, respectively to carry out electro-deposition under different voltage conditions, deposits the thick thin film (i.e. conducting polymer thin film) of about 150nm.
Preferably, in described step S1, heated overnight at reflux under the conditions of 75-80 DEG C.
Preferably, in described step S2, cryogenic conditions is-78 DEG C.Additionally in this step, mixing time is 1.5 hours.
Preferably, in described step S3, reflux under the conditions of 100 DEG C.
The present invention also provides for the preparation method of another stereochemical structure organic semiconducting materials monomer as above, its Including step:
T1, bromination reaction: substituted female ring compound is dissolved in dry THF (oxolane), bar under cryogenic conditions It is slowly added into NBS (N-bromo-succinimide) under part, stirs a period of time (such as 24 hours) under room temperature, after being spin-dried for, washing, Add dichloromethane extraction, merge organic facies, add anhydrous magnesium sulfate and be dried.Sucking filtration takes filtrate, adds (2 times of weight of filtrate) silicon Glue is spin-dried for, and crosses post and obtains solid chemical compound 1b；
T2, under cryogenic n-BuLi is added containing R1And R2The thiophene of substituent group or EDOT or EDOT derivant In THF solvent, placement is stirred at room temperature；Add ClSn (C4H9)3, react overnight under room temperature condition；Cancellation successively, extract, merge Organic facies, organic facies is washed for several times, is dried, and after being spin-dried for, distillation obtains compound 2b；
T3, Stille react: be mixed to join in toluene by compound 1b and compound 2b, be passed through N2After, at room temperature bar Add catalyst under part, reflux 16～24 hours；It is cooled to room temperature, dilutes successively, wash, merge organic facies and be dried, then add Entering silica gel to be spin-dried for, then eluting, normal-temperature vacuum is dried.
Further, in described step T1, heated overnight at reflux under the conditions of 75-80 DEG C.
Further, in described step T2, cryogenic conditions is-78 DEG C.
Further, in described step T2, mixing time is 1.5 hours.
As in figure 2 it is shown, the present invention is specifically described below by embodiment.
Embodiment 1
S1, bithiophene (5g, 35.7mmol) is dissolved in the mixed solvent of glacial acetic acid (36ml) and chloroform (10ml), room temperature Under dropwise drip Br2(28.5g, 180.56mmol), continues stirring half an hour, then heated overnight at reflux under the conditions of 78 DEG C； Cool wash with water but to after room temperature, separate out compound as white solid, then wash 3 times with water and methanol, vacuum drying under room temperature, Obtain compound as white solid 1, [M+]=455.0. (productivity: 95%)；
S2, under the cryogenic conditions of-78 DEG C, by n-BuLi (31.25ml) add EDOT (7.1g, 50mmol) THF (150ml), in solvent, it is stirred at room temperature 1.5 hours；ClSn (C is added again in mixed solvent4H9)3(50mmol, 13.56ml), React at ambient temperature overnight；Adding saturated ammonium chloride solution cancellation, dichloromethane extracts, and merges organic facies；Organic facies is used Water washs 3 use again, and anhydrous magnesium sulfate is dried, and distills after being spin-dried for；Obtain colourless oil liquid compound 2 (productivity: 93.8%)；
S3, compound 1 (1.64g, 3.63mmol) and compound 2 (9.1g, 21.00mmol) are joined 200ml THF In (THF being dried), it is passed through 30 minutes N2After, add catalyst PdCl at ambient temperature2(PPh3)2(0.673g, 0.96mmol), reflux 20 hours under the conditions of 100 DEG C；It is cooled to room temperature, adds dchloromethane, wash 3 times, merge organic Phase, organic facies anhydrous magnesium sulfate is dried, and adds silica gel and be spin-dried for, and gained compound 3 is with petroleum ether: dichloromethane=1:2 (body Long-pending ratio) it is eluent, after being spin-dried for, wash for several times with methanol and dichloromethane successively, normal temperature condition is vacuum dried, and obtains brick Red solid material 0.71g (productivity: 28.00%).
Embodiment 2
The electrochemical polymerization process of monomeric compound t-EDOT-TT is as follows:
Electrodeposition process, first adds monomeric compound t-EDOT-TT in anhydrous dichloromethane solution and is configured to The saturated solution of 0.56mM, then in solution, add electrolyte TBAPF6, making solution concentration is 0.1M.With platinum filament for electrode, Transparent glass is working electrode, and filamentary silver is the three-electrode system of reference electrode, use cyclic voltammetry electropolymerization, will (- 1.3V is to+1.3V) under the scanning speed of 100mV/s, the conducting polymer thin film of deposition is designated as P (t-EDOT-in voltage range TT)-1, under (-0.2V to 1.0V) same scanning speed under the conditions of deposit the conducting polymer thin film obtained and be designated as P (t- EDOT-TT)-2；
Embodiment 3
The cyclic voltammetry scan of monomeric compound t-EDOT-TT is as follows:
With platinum filament for electrode, transparent glass is working electrode, and filamentary silver is reference electrode, membrane structure such as Fig. 3 institute Showing, wherein, 10 is reference electrode, and 20 is to electrode, and 30 is working electrode；Cyclic voltammetry scanning obtains two kinds of film polymer The cyclic voltammetry curve of (i.e. conducting polymer thin film), such as Fig. 4 a (corresponding P (t-EDOT-TT)-1) and 4b (corresponding P (t-EDOT- TT)-2) shown in；When surface sweeping speed is 100mV/s, the oxidation starting point position of P (t-EDOT-TT)-1 is 0.26V, reduction starting point Position 0.094V.Polymer P (t-EDOT-TT)-2 oxidation starting point position under the same conditions is 0.087V, reduction starting point position- 0.1V。
Embodiment 4
The UV-vis test of monomeric compound t-EDOT-TT is as follows:
P (t-EDOT-TT)-1 maximum absorption wavelength 516nm when-0.2V, color purple, alive along with executing Raising, spectrum there occurs slightly blue shift, has obtained the thin film of redness；Colourless thin film is obtained when voltage is increased to 0.75V ,+ During 1.3V, thin film becomes light blue.P (t-EDOT-TT)-1 maximum absorption band when low-voltage is 604nm, shows bluish violet, when Voltage is increased to during 0.75V obtain colourless thin film, and during+1.2V, thin film also becomes light blue.
Monomer of the present invention and polymer preparation process are simple, and stable performance, and whole process is carried out the most in atmosphere, not Under same voltage, deposition can obtain the conducting polymer thin film of different colours, along with the rising of voltage, P (t-EDOT-TT)-1 Can convert between aubergine → redness → colourless → light blue；P (t-EDOT-TT)-2 blueness → purple → colourless → Change between light blue.
Compared with the document of report before, the present invention has obtained the polymer of two kinds of different colours changes, and P (t- EDOT-TT)-1 color in a reduction state is closer to redness, it is thus achieved that preferably red material.
The preparation method of the present invention is simple, and obtains monomer organic semiconducting materials, and has possessed different Polymerization site so that be obtained in that the compound that different loci is polymerized at different conditions, the solid type obtaining different colours gathers Laminate material.The present invention adds the derivant of thiophene or EDOT in female ring, have adjusted HOMO and the LUMO energy of material further Level, it is thus achieved that more excellent monomer material, obtains excellent stereochemical structure organic semiconductor material by the polymerization of different condition Material, and preparation process is simple and convenient, and cost is greatly reduced, and provides the foundation for application.
It should be appreciated that the application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, can To be improved according to the above description or to convert, all these modifications and variations all should belong to the guarantor of claims of the present invention Protect scope.

Claims (10)

1. a stereochemical structure organic semiconducting materials, it is characterised in that monomer whose structural formula is as follows:
Wherein, parent nucleus is the pyrroles of substituted base on thiophene, bithiophene, pyrroles, nitrogen, bithiophene, naphthalene, anthracene, three acenes, thieno Benzene or BTBT；
R1And R2One in following substituent group: H, methyl, ethyl propyl, isopropyl, direct-connected many carbon alkyl, fork chain many carbon alkane Base, cyclohexyl, face or or to fluorine cyclohexyl, alkoxyl, phenyl, trifluoromethoxy, trifluoromethylthio, face or or to fluorine or Trifluoromethoxyphen-l, face or or to fluorine or trifluoromethylthio phenyl.
2. the preparation method of a stereochemical structure organic semiconducting materials monomer as claimed in claim 1, it is characterised in that bag Include:
Step A, bromination reaction: be dissolved in the mixed solvent of glacial acetic acid and chloroform by female ring compound, dropwise drip Br under room temperature2, It is stirred for a period of time, then heated overnight at reflux；After being cooled to room temperature, washing, separate out compound as white solid, then wash number Secondary, under room temperature, vacuum drying obtains compound 1a；
Step B, under cryogenic n-BuLi is added containing R1And R2The thiophene of substituent group or EDOT or EDOT derivant In THF solvent, placement is stirred at room temperature；Add ClSn (C4H9)3, react overnight under room temperature condition；Cancellation successively, extract, merge Organic facies, organic facies is washed for several times, is dried, and after being spin-dried for, distillation obtains compound 2a；
Step C, Stille react: be mixed to join in THF solvent by compound 1a and compound 2a, be passed through N2After, at room temperature bar Add catalyst under part, reflux 16～24 hours；It is cooled to room temperature, dilutes successively, wash, merge organic facies and be dried, then add Entering silica gel to be spin-dried for, then eluting, normal-temperature vacuum is dried.
The preparation method of stereochemical structure organic semiconducting materials monomer the most according to claim 2, it is characterised in that described In step A, heated overnight at reflux under the conditions of 75-80 DEG C.
The preparation method of stereochemical structure organic semiconducting materials monomer the most according to claim 2, it is characterised in that described In step B, cryogenic conditions is-78 DEG C.
The preparation method of stereochemical structure organic semiconducting materials monomer the most according to claim 2, it is characterised in that described In step B, mixing time is 1.5 hours.
The preparation method of stereochemical structure organic semiconducting materials monomer the most according to claim 2, it is characterised in that described In step C, reflux under the conditions of 100 DEG C.
7. the preparation method of a stereochemical structure organic semiconducting materials monomer as claimed in claim 1, it is characterised in that bag Include step:
A, bromination reaction: substituted female ring compound is dissolved in dry THF, under cryogenic conditions under the conditions of add NBS, room temperature Lower stirring a period of time, after being spin-dried for, washing, add dichloromethane extraction, merge organic facies, add anhydrous magnesium sulfate and be dried, take out Leaching filtrate, adds silica gel and is spin-dried for, and crosses post and obtains solid chemical compound 1b；
B, under cryogenic n-BuLi is added containing R1And R2The thiophene of substituent group or the THF of EDOT or EDOT derivant are molten In agent, placement is stirred at room temperature；Add ClSn (C4H9)3, react overnight under room temperature condition；Cancellation successively, extract, merge organic Phase, organic facies is washed for several times, is dried, and after being spin-dried for, distillation obtains compound 2b；
C, Stille react: be mixed to join in toluene by compound 1b and compound 2b, be passed through N2After, add at ambient temperature Enter catalyst, reflux 16～24 hours；It is cooled to room temperature, dilutes successively, wash, merge organic facies and be dried, add silica gel Being spin-dried for, then eluting, normal-temperature vacuum is dried.
The preparation method of stereochemical structure organic semiconducting materials monomer the most according to claim 7, it is characterised in that described In step A, heated overnight at reflux under the conditions of 75-80 DEG C.
The preparation method of stereochemical structure organic semiconducting materials monomer the most according to claim 7, it is characterised in that described In step B, cryogenic conditions is-78 DEG C.
The preparation method of stereochemical structure organic semiconducting materials monomer the most according to claim 7, it is characterised in that institute Stating in step B, mixing time is 1.5 hours.
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Publication number Priority date Publication date Assignee Title
CN108948329A (en) * 2018-06-12 2018-12-07 合肥工业大学 A kind of conjugated polymer semiconductor material of ultralow energy level and preparation method thereof
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CN112079840A (en) * 2020-08-03 2020-12-15 浙江工业大学 Indole derivative-thiophene compound and preparation and application thereof
CN112094282A (en) * 2020-08-03 2020-12-18 浙江工业大学 Indole derivative-EDOT compound and preparation and application thereof
CN112094282B (en) * 2020-08-03 2023-06-09 浙江工业大学 Indole derivative-EDOT compound and preparation and application thereof
CN112079840B (en) * 2020-08-03 2023-06-27 浙江工业大学 Indole derivative-thiophene compound and preparation and application thereof
CN112079849A (en) * 2020-08-14 2020-12-15 浙江工业大学 Indole derivative-proEDOT compound and preparation and application thereof
CN112079849B (en) * 2020-08-14 2023-06-27 浙江工业大学 Indole derivative-proEDOT compound and preparation and application thereof

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