CN104672434B - A kind of organic semiconducting materials and preparation method and application - Google Patents
A kind of organic semiconducting materials and preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of organic semiconducting materials, containing 4,4 ' double the triazolyl benzene thiophene units of 1H 1,2,3 and aromatic group, aromatic group and 4,4 ' double triazolyl benzene thiophene units of 1H 1,2,3 are connected with conjugated manner.The invention also discloses the preparation method of above-mentioned organic semiconducting materials, by by being prepared from containing double alkynyl benzene thiophene monomers and the alkyl chain containing azido by click chemistry.Compared with prior art, organic semiconducting materials of the invention are conducive to intermolecular π pi accumulations, and the flatness for making polymer more preferably, is conducive to the raising of device performance；The preparation method of the present invention is simple and convenient, and yield is high, and post processing is simple, is easy to purification.
Description
Technical field
The present invention relates to organic photoelectrical material technical field, more particularly to a kind of organic semiconducting materials and preparation method thereof
And application.
Background technology
In the world today, the problem of energy problem pays close attention to jointly as the whole mankind.With non-renewable fossil energy
Constantly consumption, the continuous deterioration of problem of environmental pollution, people forwardly seek and develop various reproducible clean energy resourcies.
Wherein, because solar energy is inexhaustible, with its clean energy resource not to the utmost, the solar cell converted solar energy into electrical energy is ground
Study carefully the great attention for receiving various countries.In recent years, organic photovoltaic devices have a light weight because of it, and processing is simple, cost it is low and
Many advantages, such as flexible device of large area can be made, the study hotspot as solar cell, wherein the single polymer layer sun electricity
Pond highest energy conversion efficiency alreadys exceed 10% (DOI:10.1038/ncomms6293), with very vast business application
Prospect.
Relative to inorganic semiconductor solar cell, the efficiency of organic photovoltaic cell or relatively low.Turn to improve its photoelectricity
Efficiency is changed, scientists pass through the optimization of materials chemistry structure, the optimization of device architecture, the regulation and control multi-angle of device preparation condition
Start with, conduct in-depth research.Wherein, the improvement of photoactive layer material, especially to the optimization of conjugated polymer structure with
Adjustment, is the research emphasis of polymer solar cells.In recent years, it is widely used in the conjugation of polymer solar cells photoactive layer
Polymer is designed and is synthesized, and achieves corresponding progress with breaking through.As benzene thiophene (BDT) unit is used as one kind
The conjugated molecule structure of symmetry, is widely used in photoelectric field, and the mobility of the field-effect transistor based on BDT units reaches
0.25cm2V-1s-1, the single polymer layer solar cell based on BDT units develops into current efficiency and reached 8-9%
(Energy Environ.Sci.,2012,5,8208；Nat.Photon.2012,6,591；Adv.Mater.2013,25,
4944–4949；J.Am.Chem.Soc.2013,135,17060-17068；J.Am.Chem.Soc.2013,135,4656-
4659).Therefore, it is most important to development polymer solar cells to design and develop new conjugated polymer unit and material
, this will lay firm basis for the commercialization of organic photovoltaic battery in the near future.
The content of the invention
In order to overcome the disadvantages mentioned above and deficiency of prior art, an object of the present invention is that offer one kind is organic and partly led
Body material, the flatness for making polymer more preferably, improves the mobility of its electric charge, is conducive to the transmission of electric charge, is expected to obtain more preferably
Device performance.
The second object of the present invention is the preparation method for providing above-mentioned organic semiconducting materials, simple and convenient, and yield is high,
Post processing is simple, is easy to purification.
The third object of the present invention is the application for providing above-mentioned organic semiconducting materials.
The purpose of the present invention is achieved through the following technical solutions：
A kind of organic semiconducting materials, its structural formula is as follows：
Wherein, Ar is electron deficient conjugate unit；π is the conjugate unit containing carbon-carbon double bond, carbonnitrogen bond；0<x<1,0<y<
1, x+y=1；M is 0 to 10000 natural number；N is 1 to 10000 natural number；
R1For the alkyl chain with 1 to 30 carbon numbers.
The Ar is ethenylidene, ethynylene, arlydene, heteroarylidene or passes through singly linked 2-6 arlydene
The group formed；Or, Ar is ethenylidene, ethynylene, arlydene, heteroarylidene or individual by singly linked 2-6
One or more of arlydene carbon atom is by oxygen atom, alkenyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyanogen
Base or nitro substitution, hydrogen atom is by halogen atom, oxygen atom, alkenyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyanogen
Base or nitro replace the group to be formed.
The Ar be diazosulfide, BTA, naphtho- thiadiazoles, aphthotriazoles, pyrrolo-pyrrole-dione, it is indigo,
Bioxindol, quinoxaline, benzene-naphthalene diimide, perylene diimides, thieno acid imide or quinoxaline.
The Ar is one kind in following structure：
Wherein, R is hydrogen or the alkyl with 1~30 carbon atom；Or be the alkyl with following structure：One in alkyl
Individual or multiple carbon atoms are taken by oxygen atom, alkenyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyano group or nitro
Generation, hydrogen atom is taken by halogen atom, oxygen atom, alkenyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyano group or nitro
Generation.
The π be benzene, naphthalene, thiophene, bithiophene, selenophen, tellurium fen, furans, pyrroles, thiophene cough up, thiazole, oxazole or triazole.
The π is one kind in following structure：
Wherein, R is hydrogen or the alkyl with 1~30 carbon atom；Or be the alkyl with following structure：One in alkyl
Individual or multiple carbon atoms are taken by oxygen atom, alkenyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyano group or nitro
Generation, hydrogen atom is taken by halogen atom, oxygen atom, alkenyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyano group or nitro
Generation.
The R1For the alkyl chain with 1 to 30 carbon numbers, wherein, one or more of alkyl chain carbon atom is by oxygen
Atom, alkenyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyano group or nitro substitution, hydrogen atom is by halogen atom quilt
Oxygen atom, alkenyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyano group or nitro substitution.
The preparation method of the organic semiconducting materials, comprises the following steps：
(1) under cupprous catalytic action click chemistry is occurred into for the compound shown in the compound shown in formula 2 and formula 3
Reaction, obtains the compound shown in formula 4；
Wherein, Y be hydrogen atom, trimethyl silicon substrate or triisopropylsilyl, X be hydrogen atom, halogen atom, boric acid base group,
Borate group or trialkyltin groups；R2Definition be equal to R1；
(2) using the compound shown in formula 4 as raw material, organic semiconducting materials as shown in Equation 1 are synthesized by polymerisation.
Application of the organic semiconducting materials in organic electro-optic device.
Compared with prior art, the present invention has advantages below and beneficial effect：
1st, organic semiconducting materials of the invention, containing 4,4 '-bis- 1H-1,2,3- triazolyl benzene thiophene structures are introduced
Aromatic group Ar and the π unit of functionalization, has expanded the application of this kind of material.
2nd, organic semiconducting materials of the invention, by 1H-1,2,3- triazole rings are incorporated into benzene thiophene unit, 1H-
The introducing of 1,2,3-triazoles ring, is conducive to intermolecular pi-pi accumulation, and the flatness for making polymer more preferably, improves moving for its electric charge
Shifting rate, is conducive to the transmission of electric charge, is expected to obtain more preferable device performance.
3rd, the preparation method of organic semiconducting materials of the invention, dexterously using click chemistry (Click
Chemistry) by 1H-1,2,3- triazole rings are incorporated into conjugated polymer, and synthetic method uses " one kettle way ", simple and convenient,
Yield height (more than 90%), post processing is simple, is easy to purification.
Brief description of the drawings
Fig. 1 is embodiments of the invention resulting polymers PTRI12-DPP12, PTRI16-DPP12, PTRI20-DPP12
Thermogravimetic analysis (TGA) figure.
Fig. 2 is embodiments of the invention resulting polymers PTRI12-DPP20, PTRI16-DPP20, PTRI20-DPP20
Thermogravimetic analysis (TGA) figure.
Fig. 3 is that embodiments of the invention resulting polymers PTRI12-DPP12, PTRI16-DPP12, PTRI20-DPP12 exist
CHCl3Abosrption spectrogram in solution.
Fig. 4 is embodiments of the invention resulting polymers PTRI12-DPP12, PTRI16-DPP12, PTRI20-DPP12
Film absorption spectrogram.
Fig. 5 is that embodiments of the invention resulting polymers PTRI12-DPP20, PTRI16-DPP20, PTRI20-DPP20 exist
CHCl3Abosrption spectrogram in solution.
Fig. 6 is embodiments of the invention resulting polymers PTRI12-DPP20, PTRI16-DPP20, PTRI20-DPP20
Film absorption spectrogram.
Fig. 7 be embodiments of the invention resulting polymers PTRI12-DPP12, PTRI16-DPP12, PTRI20-DPP12,
PTRI12-DPP20, PTRI16-DPP20, PTRI20-DPP20 oxidation potential curve ratio are relatively schemed.
Fig. 8 be embodiments of the invention resulting polymers PTRI12-DPP12, PTRI16-DPP12, PTRI20-DPP12,
Solar cell device J-V curve maps prepared by PTRI12-DPP20, PTRI16-DPP20, PTRI20-DPP20.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
The practice of the present invention can use the routine techniques of the polymer chemistry in art technology.In the examples below,
The accuracy of numeral (including amount, temperature, reaction time etc.) used is endeavoured to ensure, it is contemplated that some experimental errors and deviation.
Temperature used to be DEG C to represent in the examples below, and pressure is atmospheric pressure or close to atmospheric pressure.All solvents be analysis level or
Chromatographic grade is bought, and all reactions are carried out under argon inert atmosphere.Unless otherwise noted, otherwise all reagents are all business
Obtain.
Embodiment 1,4,4 '-(2,6- dibromo benzos [1,2-B:4,5-B'] Dithiophene -4,8- diyls) it is double that (1-2- butyl is pungent
Base) -1H-1,2,3- triazoles) (referred to as DBrTRI12) synthesis
Chemical reaction flow is shown below, and specific reactions steps and reaction condition are as follows：
Wherein, (I) oxalyl chloride, dichloromethane, room temperature 12 hours；(II) dimethylamine hydrochloride, three second, dichloromethane, room temperature 12
Hour；(III) NBS, DMF, room temperature 6 hours；(IV) -78 DEG C, tetrahydrofuran, n-BuLi, room temperature 12 hours；(V) -78 DEG C,
Trimethyl silicane ethyl-acetylene, tetrahydrofuran recovers to room temperature 1 hour, then adds anhydrous stannous chloride, 50 DEG C, 12 hours；(Ⅵ)
Azido alkyl chain, Anhydrous potassium carbonate, cuprous iodide, tetrahydrofuran, water, acetonitrile, backflow.
(1) 2,5- for synthesizing the method [Polymer 54, (2013), 2278-2284] according to disclosed in Long Liang
Dibromo thiophene -3- acid dimethvlamides (compound 3,15.6g, 50mmol) are dissolved into anhydrous tetrahydro furan (120mL),
Under the conditions of -78 DEG C, n-BuLi (20mL, 2.5M) is added dropwise in above-mentioned reaction system, is then slowly warmed to room temperature
And be kept stirring for staying overnight.Reaction terminates, and reaction solution is directly poured into the aqueous ammonium chloride solution of saturation, and suction filtration is simultaneously washed with acetonitrile
3 times.THF is used after solvent is removed:Acetonitrile (1:1) recrystallized, obtain orange-yellow acicular crystal (compound 4,3.8g,
Yield 40.2%).
The nuclear magnetic data of product is as follows：1H NMR(300MHz,CDCl3),δ(ppm):7.60(s,2H).
(2) under argon gas protection, trimethyl silicane ethyl-acetylene (2.3g, 22.5mmol) is dissolved in anhydrous tetrahydro furan (50mL)
In.Under the conditions of -78 DEG C, n-BuLi (9mL, 2.5M) is added dropwise in above-mentioned reaction system, in reacting 2 at -78 DEG C
Hour, compound 4 (1.89g, 5mmol) is then added, is slowly warmed to room temperature and is kept stirring for 5 hours.Then add in room temperature
Enter anhydrous stannous chloride (7.56g, 40mmol), be warming up to 50 DEG C of reactions and stay overnight.Reaction terminates, and reaction solution is directly spin-dried for, gained
Solid is using petroleum ether as eluant, eluent, and silica gel crosses post, obtains greenish yellow solid (compound 5,1.62g, yield 60%).
The nuclear magnetic data of product is as follows：1H NMR(600MHz,CDCl3),δ(ppm):7.52(s,2H),0.35(s,18H)
.13C NMR (150MHz, CDCl3),δ(ppm)：141.76,137.63,125.92,117.60,110.21,106.40,99.47,
0.0005.
(3) by compound 5 (1.08g, 2mmol), 5- (azido-methyl) hendecane (1.69g, 8mmol), Anhydrous potassium carbonate
(2.2g, 16mmol), cuprous iodide (200mg) is placed in 150mL reaction bulbs, adds THF (60mL), water (2mL), acetonitrile
(2mL).Under argon gas protection, back flow reaction is heated to 3 days.Using silica gel plate point plate, the situation of reaction is monitored.Finally, react
Terminate, by reaction solution quickly through short column of neutral alumina, remove metal salt.Gained solid after solvent is removed to be tied again with methanol
Crystalline substance, obtains pale yellow powder (DBrTRI12,1.59g, 91.5%).
The nuclear magnetic data of product is as follows：1H NMR(600MHz,CDCl3),δ(ppm):8.05(s,2H).7.95(s,2H),
4.44(d,4H),2.07(m,2H),1.36-1.25(m,32H),0.93-0.87(m,12H).13C NMR(150MHz,CDCl3),
δ(ppm):144.27,138.53,135.09,126.10,123.15,118.18,117.45,54.36,39.22,31.77,
31.45,31.13,29.55,28.57,26.37,22.93,22.65,14.09,14.05.
Embodiment 2,4,4 '-(2,6- dibromo benzos [1,2-B:4,5-B'] Dithiophene -4,8- diyls) double (1-2- hexyl last of the ten Heavenly stems
Base) -1H-1,2,3- triazoles) (referred to as DBrTRI16) synthesis
Synthetic method is consistent with embodiment 1.Obtain pale yellow powder (DBrTRI16,1.7g, 92%).
The nuclear magnetic data of product is as follows：1H NMR(600MHz,CDCl3),δ(ppm):8.05(s,2H).7.96(s,2H),
4.44(d,4H),2.07(m,2H),1.36-1.25(m,48H),0.89-0.85(m,12H).13C NMR(150MHz,CDCl3),
δ(ppm):144.23,138.49,135.05,126.10,123.17,118.15,117.42,54.38,39.23,31.88,
31.78,31.46,31.45,29.89,29.55,29.54,29.30,26.39,26.36,22.68,22.65,14.11,
14.09.
Embodiment 3,4,4 '-(2,6- dibromo benzos [1,2-B:4,5-B'] Dithiophene -4,8- diyls) double (1-2- octyl groups ten
Dialkyl group) -1H-1,2,3- triazoles) (referred to as DBrTRI20) synthesis
Synthetic method is consistent with embodiment 1.Obtain pale yellow powder (DBrTRI20,2.0g, 95%).
The nuclear magnetic data of product is as follows：1H NMR(600MHz,CDCl3),δ(ppm):8.05(s,2H),7.96(s,2H),
4.44(d,4H),2.07(m,2H),1.36-1.25(m,64H),0.89-0.85(m,12H).13C NMR(150MHz,CDCl3),
δ(ppm):144.26,138.51,135.07,126.12,123.14,118.17,117.43,54.38,39.23,31.91,
31.88,31.45,29.88,29.65,29.63,29.59,29.54,29.35,29.30,26.40,22.69,22.68,
22.65,14.11,14.09.
The synthesis of embodiment 4, polymer
Polymerisation flow chart is shown below, and specific steps and reaction condition are as follows：
Wherein, (I) toluene, Pd2(dba)3, P (o-tol)3, aqueous potassium phosphate solution, A336, microwave reaction, 140 DEG C, 45 points
Clock.
(1) polymer P TRI12-DPP12 synthesis
Monomer DBrTRI12 (163.8mg, 0.2mmol) is weighed, monomer DPP12 (177.8mg, 0.2mmol) is anti-in microwave
Ying Guanzhong, adds toluene (3mL), and potassium phosphate 85mg, deionized water (0.5mL), A336 (1 drop) leads to argon gas 20 minutes.It is then fast
Speed adds catalyst and part, Pd2(dba)3(3mg), P (o-tol)3(6mg), logical argon gas makes to be full of argon gas in reaction tube, lid
Good lid, carries out microwave reaction, is reacted 45 minutes in 140 DEG C.Reaction terminates, and reaction solution is instilled in methanol and separates out polymer,
Then polymer acetone is washed in apparatus,Soxhlet's, filtering head, finally dried polymer in vacuum drying chamber, most
230mg polymer (PTRI12-DPP12), yield 89% are obtained eventually.It is with GPC (polystyrene the is standard specimen) molecular weight measured
Mn=15.1kDa, PDI=1.8.
(2) polymer P TRI16-DPP12 synthesis
Polymerizing condition is consistent with the above.Yield 86%.The molecular weight measured with GPC (polystyrene is standard specimen) is Mn=
14.0kDa, PDI=1.5.
(3) polymer P TRI20-DPP12 synthesis
Polymerizing condition is consistent with the above.Yield 85%.The molecular weight measured with GPC (polystyrene is standard specimen) is Mn=
13.0kDa, PDI=1.5.
(4) polymer P TRI12-DPP20 synthesis
Polymerizing condition is consistent with the above.Yield 85%.The molecular weight measured with GPC (polystyrene is standard specimen) is Mn=
24.2kDa, PDI=1.4.
(5) polymer P TRI16-DPP20 synthesis
Polymerizing condition is consistent with the above.Yield 82%.The molecular weight measured with GPC (polystyrene is standard specimen) is Mn=
25.4kDa, PDI=1.8.
(6) polymer P TRI16-DPP20 synthesis
Polymerizing condition is consistent with the above.Yield 82%.The molecular weight measured with GPC (polystyrene is standard specimen) is Mn=
11.2kDa, PDI=1.6.
Fig. 1 and Fig. 2 are respectively embodiment 4 resulting polymers PTRI12-DPP12, PTRI16-DPP12, PTRI20-
DPP12, PTRI12-DPP20, PTRI16-DPP20, PTRI20-DPP20 thermogravimetic analysis (TGA) figure.It can be seen that complete
Portion's polymer all has preferable heat endurance, and decomposition temperature is respectively：327℃、323℃、315℃、340℃、336℃、311
℃。
Fig. 3 and Fig. 4 are embodiment 4 resulting polymers PTRI12-DPP12, PTRI16-DPP12, PTRI20-DPP12 respectively
Solution and film absorption spectrogram, it can be seen that polymer shows similar absworption peak, its solution absorption peak is about
For 410 nanometers, 680 nanometers；Absworption peak in the film is respectively 420 nanometers, 700 nanometers.Wherein, film absorption spectrogram
ABSORPTION EDGE is close to 900 nanometers, and there are obvious red shift, the light of red shift in the corresponding film absorption side of each polymer than solution ABSORPTION EDGE
Spectrum is beneficial to the raising of photoelectric transformation efficiency.
Likewise, Fig. 5 and Fig. 6 be respectively the resulting polymers PTRI12-DPP20 of embodiment 4, PTRI16-DPP20,
PTRI20-DPP20 solution and film absorption spectrogram.
From formula calculate polymer P TRI12-DPP20, PTRI16-DPP20, PTRI20-DPP20, PTRI12-DPP12,
PTRI16-DPP12, PTRI20-DPP12 optics with gaps EgRespectively：1.37eV、1.39eV、1.37eV、1.38eV、
1.37eV、1.39eV。
Fig. 7 is embodiment 4 resulting polymers PTRI12-DPP12, PTRI16-DPP12, PTRI20-DPP12, PTRI12-
DPP20, PTRI16-DPP20, PTRI20-DPP20 oxidation potential curve ratio are relatively schemed.Polymer P TRI12- is calculated to obtain from formula
DPP20, PTRI16-DPP20, PTRI20-DPP20, PTRI12-DPP12, PTRI16-DPP12, PTRI20-DPP12 HOMO
Energy level is respectively -5.41eV, -5.42eV, -5.41eV, -5.37eV, -5.39eV, -5.40eV.LOMO energy levels are respectively-
3.96eV、-3.96eV、-3.96eV、-3.95eV、-3.95eV、-3.96eV.As can be seen that obtain deep HOMO energy levels simultaneously,
LOMO energy levels are also moved down simultaneously.
Fig. 8 is embodiment 4 resulting polymers PTRI12-DPP12, PTRI16-DPP12, PTRI20-DPP12, PTRI12-
Solar cell device J-V curve maps prepared by DPP20, PTRI16-DPP20, PTRI20-DPP20.Device architecture is upside-down mounting knot
Structure：ITO/PFN/Polymer:PC71BM(1:2)/MoO3/Al.After the DIO of addition 3%, the short circuit electricity of efficiency highest device
It is respectively 2.58mA/cm to flow (Jsc) and open-circuit voltage (Voc)2And 0.70V, energy conversion efficiency is 1.01%.Detailed data is shown in
Table 1.
Device fabrication process is as follows：First, on cleaned ITO one layer of 5~10nm of spin coating PFN films, then will
The polymeric material and PC prepared in advance71BM (mass ratioes 1:2, plus 3%DIO) chlorobenzene solution is got rid of in PFN by spin-coating film
On, then wet film is dried, untill film is dried.~10nm MoO is deposited finally by thermal evaporation3With~
70nm Al is used as anode.The effective area of device is 0.16cm2.Performance survey is carried out after device is encapsulated in atmospheric environment
Examination.The energy conversion efficiency and electric current (J) of device-voltage (V) characteristic curve are obtained under AM 1.5G solar simulators.Simulation
The power of sunlamp is demarcated with standard silicon solar cell before testing, is 100mW cm-2。
Specific solar cell device efficiency (device architecture as shown in table 1：ITO/PFN/Polymer:PC71BM(1:2)(CB+
3%DIO) (90nm)/MoO3/ Al), it may be seen that by using the invention of this patent, successfully by 4,4 '-bis- 1H-1,2,
3- triazolyl benzene thiophene units introduce polymer, and obtain a series of polymer, illustrate the feasibility of the present invention
With containing 4,4 '-organic semiconducting materials of bis- 1H-1,2,3- triazolyls benzene thiophene units organic electro-optic device application
Potentiality.
The device architecture of table 1：ITO/PFN/Polymer:PC71BM(1:2) (CB+3%DIO) (90nm)/MoO3/Al
| Polymer | PCE (%) | Jsc(mA/cm2) | Voc(V) | FF (%) |
| PTRI12-DPP12 | 0.33 | 1.75 | 0.72 | 25.86 |
| PTRI16-DPP12 | 0.94 | 2.43 | 0.72 | 53.51 |
| PTRI20-DPP12 | 1.01 | 2.58 | 0.70 | 55.83 |
| PTRI12-DPP20 | 0.50 | 2.06 | 0.64 | 38.00 |
| PTRI16-DPP20 | 0.64 | 2.03 | 0.67 | 47.49 |
| PTRI20-DPP20 | 0.79 | 2.19 | 0.67 | 54.05 |
Above-described embodiment is preferably embodiment, but embodiments of the present invention are not by the embodiment of the invention
Limitation, other any Spirit Essences without departing from the present invention and the change made under principle, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (8)
1. a kind of preparation method of organic semiconducting materials, it is characterised in that
The structural formula of the organic semiconducting materials is as follows：
Wherein, Ar is electron deficient conjugate unit；π is the conjugate unit containing carbon-carbon double bond, carbonnitrogen bond；0<x<1,0<y<1, x+
Y=1；M is 0 to 10000 natural number；N is 1 to 10000 natural number；
R1For the alkyl chain with 1 to 30 carbon numbers；
The preparation method of the organic semiconducting materials comprises the following steps：
(1) compound shown in the compound shown in formula 2 and formula 3 under cupprous catalytic action to that click chemistry occur anti-
Should, obtain the compound shown in formula 4；
Wherein, Y is hydrogen atom, trimethyl silicon substrate or triisopropylsilyl, and X is hydrogen atom, halogen atom, boric acid base group, boric acid
Ester group or trialkyltin groups；R2Definition be equal to R1；
(2) using the compound shown in formula 4 as raw material, organic semiconducting materials as shown in Equation 1 are synthesized by polymerisation.
2. the preparation method of organic semiconducting materials according to claim 1, it is characterised in that the Ar is sub- ethene
Base, ethynylene, arlydene, heteroarylidene or the group formed by singly linked 2-6 arlydene；Or, Ar is
Ethenylidene, ethynylene, arlydene, heteroarylidene pass through one or more of singly linked 2-6 arlydene carbon
Atom is replaced by oxygen atom, alkenyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyano group or nitro, hydrogen atom quilt
Halogen atom, oxygen atom, alkenyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyano group or nitro replace the base to be formed
Group.
3. the preparation method of organic semiconducting materials according to claim 1, it is characterised in that the Ar is benzo thiophene two
Azoles, BTA, naphtho- thiadiazoles, aphthotriazoles, pyrrolo-pyrrole-dione, indigo, bioxindol, quinoxaline, benzene-naphthalene diimide,
Perylene diimides, thieno acid imide or quinoxaline.
4. the preparation method of organic semiconducting materials according to claim 1, it is characterised in that the Ar is following structure
In one kind：
Wherein, R is hydrogen or the alkyl with 1~30 carbon atom；Or be the alkyl with following structure：In alkyl one or
Multiple carbon atoms are replaced by oxygen atom, alkenyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyano group or nitro, hydrogen
Atom is replaced by halogen atom, oxygen atom, alkenyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyano group or nitro.
5. the preparation method of organic semiconducting materials according to claim 1, it is characterised in that the π is benzene, naphthalene, thiophene
Fen, bithiophene, selenophen, tellurium fen, furans, pyrroles, thiophene are coughed up, thiazole, oxazole or triazole.
6. the preparation method of organic semiconducting materials according to claim 1, it is characterised in that the π is following structure
In one kind：
Wherein, R is hydrogen or the alkyl with 1~30 carbon atom；Or be the alkyl with following structure：In alkyl one or
Multiple carbon atoms are replaced by oxygen atom, alkenyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyano group or nitro, hydrogen
Atom is replaced by halogen atom, oxygen atom, alkenyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyano group or nitro.
7. the preparation method of organic semiconducting materials according to claim 1, it is characterised in that the R1For with 1 to 30
The alkyl chain of carbon number, wherein, one or more of alkyl chain carbon atom by oxygen atom, alkenyl, alkynyl, aryl, hydroxyl,
Amino, carbonyl, carboxyl, ester group, cyano group or nitro substitution, hydrogen atom is by halogen atom by oxygen atom, alkenyl, alkynyl, aryl, hydroxyl
Base, amino, carbonyl, carboxyl, ester group, cyano group or nitro substitution.
8. the organic semiconductor material that the preparation method of organic semiconducting materials according to claim 1~7 any one is obtained
Expect the application in organic electro-optic device.
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