CN113493559A - Preparation and application of cyclized indigo receptor and polymer - Google Patents

Preparation and application of cyclized indigo receptor and polymer Download PDF

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CN113493559A
CN113493559A CN202010195051.XA CN202010195051A CN113493559A CN 113493559 A CN113493559 A CN 113493559A CN 202010195051 A CN202010195051 A CN 202010195051A CN 113493559 A CN113493559 A CN 113493559A
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indigo
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刘云圻
杨杰
蒋雅倩
朱明亮
陈金佯
匡俊华
郭云龙
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Abstract

The invention discloses a cyclized indigo receptor and a preparation method and application of a polymer. The structure of the polymer is shown as a formula I, wherein R is C1～C40Linear or branched alkyl. The invention also provides a preparation method of the polymer shown in the formula I. The raw materials of the invention are commercial products; the synthetic route is simple and efficient. The hole mobility of an organic field effect transistor prepared by taking the novel cyclized indigo polymer as an organic semiconductor layer is up to 1.22cm2V‑ 1s‑1The electron mobility is 0.80cm at most2V‑1s‑1The preparation method has good application prospect in bipolar organic field effect transistor devices.

Description

Preparation and application of cyclized indigo receptor and polymer
Technical Field
The invention belongs to the field of materials, and particularly relates to a preparation method and application of a cyclized indigo receptor and a polymer.
Background
Organic field effect transistors (abbreviated as OFETs) are active devices which use conjugated organic semiconductor materials as semiconductor layers and control the conductivity of the materials by vertical electric fields. OFETs are key unit devices of organic circuits, have the advantages of solution-method processing, good flexibility, easy adjustment of photoelectric properties and the like, and have important application prospects in devices such as logic circuits, sensors, driving displays and the like.
The OFETs semiconductor material comprises an organic small molecule material and a high molecular polymer material. The high molecular polymer material has the advantages of light weight, good flexibility, large-area printing and processing and the like, and has attracted extensive attention of scientific researchers. The design and synthesis of novel polymeric semiconductor materials are of great significance to the development of the field. Most of the current high-performance OFETs materials are p-type materials, and the development of bipolar materials is relatively delayed.
Disclosure of Invention
One of the objectives of the present invention is to provide a cyclized indigo (BAI) receptor and polymer.
The structural general formula of the BAI polymer provided by the invention is shown as formula I:
Figure RE-GDA0002503659130000011
in the formula I, R is a straight chain or branched chain alkyl group with the total number of carbon atoms of 1-40, specifically can be a straight chain or branched chain alkyl group with the total number of carbon atoms of 16-36, and more specifically can be 2-decyl tetradecyl;
ar is the following group:
Figure RE-GDA0002503659130000012
Figure RE-GDA0002503659130000021
represents a substitution bit;
n is the degree of polymerization, and n is 5 to 100, specifically n may be 10 to 70, more specifically 26.
The polymer shown in the formula I can be polymer P2F2 ClBAI-V;
the structural formula of the polymer P2F2ClBAI-V is as follows:
Figure RE-GDA0002503659130000022
wherein R is 2-decyl tetradecyl;
n is 26.
The polymer shown in the formula I is prepared by a method comprising the following steps:
carrying out polymerization reaction on a compound shown as a formula VII and a bistin compound under the action of a catalyst and a ligand to obtain a polymer shown as a formula I;
Figure RE-GDA0002503659130000023
in formula VII, R is as defined above for R in formula I.
In the above method, the bistin compound is as follows:
Figure RE-GDA0002503659130000024
the catalyst may be selected from: at least one of tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) palladium dichloride, and tris (dibenzylideneacetone) dipalladium;
the ligand may be selected from: at least one of triphenylphosphine, tri (o-tolyl) phosphine, and triphenylarsine.
The feeding mole fraction of the compound shown in the formula VII is 1.00 part;
the feeding mole fraction of the bistin compound can be 0.95-1.05; specifically, the amount of the compound is 1.00 part;
the feeding mole fraction of the catalyst can be 0.01-0.10; specifically, 0.03 part;
the feeding mole fraction of the ligand can be 0.04-0.80; specifically, 0.24 part;
in the step of polymerization reaction, the temperature can be 90-140 ℃; specifically, the temperature can be 130 ℃;
the reaction time can be 1-80 hours; specifically, the time period may be 60 to 80 hours, more specifically 72 hours;
the feeding molar ratio of the compound shown in the formula VII, the bistin compound, the catalyst and the ligand can be specifically 1.0: 1.0: 0.03: 0.24;
the polymerization reaction may be carried out in a solvent;
the solvent may be selected from: at least one of toluene, chlorobenzene, and xylene.
The method can further comprise the following purification steps:
after the polymerization reaction is finished, cooling the obtained reaction system, sequentially adding concentrated hydrochloric acid and methanol, stirring and filtering at room temperature, sequentially extracting the obtained precipitate with methanol, acetone and n-hexane by using a Soxhlet extractor until the precipitate is colorless, removing micromolecules and a catalyst, and extracting with trichloromethane to obtain the product; wherein, the volume ratio of the methanol to the concentrated hydrochloric acid is specifically 20:1, the concentration of concentrated hydrochloric acid may be 12M.
In addition, the starting material of the compound shown in the formula VII is also within the protection scope of the present invention.
Figure RE-GDA0002503659130000031
In formula VII, R is as defined for R in formula I.
The compound shown in the formula VII is prepared by a method comprising the following steps:
a) carrying out nitration reaction on the 4-chloro-3-fluorobenzaldehyde in a mixed solution of concentrated sulfuric acid and concentrated nitric acid to obtain 4-chloro-5-fluoro-2-nitrobenzaldehyde shown in a formula II;
Figure RE-GDA0002503659130000032
b) reacting the 4-chloro-5-fluoro-2-nitrobenzaldehyde shown in the formula II obtained in the step a), acetone and water in a sodium hydroxide solution to obtain difluorodichloroindigo shown in the formula III (namely 2F2 Cl-indigo);
Figure RE-GDA0002503659130000041
c) carrying out condensation reaction on the difluorodichloroindigo shown in the formula III obtained in the step b) and 2-thiopheneacetyl chloride to obtain difluorodichlorocycloindigo (namely 2F2ClBAI) shown in the formula IV;
Figure RE-GDA0002503659130000042
d) brominating the difluorodichlorocyclization indigo shown in the formula IV obtained in the step c) to obtain difluorodichlorocyclization indigo-dibromo (namely 2F2ClBAI-2Br) shown in the formula V;
Figure RE-GDA0002503659130000043
e) performing coupling reaction on the difluorodichlorocyclization indigo-dibromide shown in the formula V obtained in the step d) and a compound a to obtain difluorodichlorocyclization indigo-dithiophene shown in the formula VI;
Figure RE-GDA0002503659130000051
in the compound a, R is the same as the definition of R in the formula I;
in formula VI, R is as defined for R in formula I;
f) brominating difluorodichlorocyclization indigo-dithiophene obtained in the step e) and shown in the formula VI to obtain difluorodichlorocyclization indigo-dithiophene-dibromo shown in the formula VII.
In the step a) of the method, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid can be 20-4: 1, specifically 8.75: 1;
the proportion of the 4-chloro-3-fluorobenzaldehyde to the concentrated sulfuric acid or the concentrated nitric acid can be 0.016 mol: 8.75 mL: 1 mL;
in the reaction step, the temperature can be-20-60 ℃, and the time can be 2-48 hours;
in step b), the volume ratio of water to acetone may be 1: 0.5-5, specifically 1: 2.3;
the molar ratio of the 4-chloro-5-fluoro-2-nitrobenzaldehyde shown in the formula II to the sodium hydroxide can be 1: 0.5-4, specifically 1: 1.2;
in the reaction step, the temperature can be-20-40 ℃, and the time can be 1-60 hours;
in the step c), the feeding molar dosage ratio of the difluorodichloroindigo to the 2-thiopheneacetyl chloride can be 1: 2.0-8.0, and specifically can be 1: 4; in the reaction step, the temperature can be 100-150 ℃, and the time can be 4-48 hours;
the reaction is carried out in an organic solvent, and the organic solvent can be o-xylene;
in the step d), the bromination reaction is carried out in the presence of a bromination reagent; the brominating agent can be N-bromosuccinimide (namely NBS); the bromination reaction can be carried out in an organic solvent, and the organic solvent can be chloroform;
the feeding molar ratio of the difluorodichlorocyclization indigo to the N-bromosuccinimide can be 1: 2.0-2.6, and specifically can be 1: 2.3; in the reaction step, the temperature can be-10-40 ℃, and the time can be 2-48 hours;
in the step e), the coupling reaction is carried out under the catalysis of tris (dibenzylideneacetone) dipalladium and tris (o-tolyl) phosphine;
the feeding molar usage ratio of the difluorodichlorocyclization indigo-dibromide to the compound a can be 1: 2.0-6.0, and specifically can be 1: 2.4; in the reaction step, the temperature can be 80-140 ℃, and the time can be 1-48 hours;
the reaction is carried out in an organic solvent,
the organic solvent can be at least one selected from toluene, chlorobenzene and dimethyl sulfoxide;
in the step f), the bromination reaction is carried out in the presence of a bromination reagent; the brominating agent can be N-bromosuccinimide (namely NBS); the bromination reaction can be carried out in an organic solvent, and the organic solvent can be chloroform;
the feeding molar ratio of the difluorodichlorocyclization indigo-dithiophene to the N-bromosuccinimide can be 1: 2.0-2.6, and specifically can be 1: 2.3; in the reaction step, the temperature can be-10-40 ℃ and the time can be 2-48 hours.
When R in the compound shown in the formula VII is 2-decyl tetradecyl, the synthetic route of the compound shown in the formula VII is shown in figure 1.
The invention also aims to provide application of the polymer shown in the formula I, namely application of the polymer shown in the formula I in preparing organic field effect transistors;
in the above application, the polymer represented by the formula I is used as an organic semiconductor layer of an organic field effect transistor;
the organic field effect transistor may be a bipolar organic field effect transistor.
The invention further aims to provide an organic field effect transistor which takes the polymer shown in the formula I as an organic semiconductor layer.
The invention has the advantages that:
1. the raw materials are commercial products, the synthetic route is simple, the monomers and the polymers are new molecules, and meanwhile, the method can be popularized to the synthesis of various linear chain or branched chain fluorochloro cyclized indigo polymers;
2. the HOMO and LUMO energy levels of the fluorochloro cyclized indigo polymer are matched with those of a gold electrode, so that the fluorochloro cyclized indigo polymer can be used for preparing a high-performance bipolar field effect transistor device;
3. the organic field effect transistor prepared by using the fluorochlorocycloindigo blue polymer as a semiconductor layer has higher mobility and on-off ratio (the highest hole mobility is 1.22 cm)2V-1s-1The electron mobility is 0.80cm at most2V-1s-1) And has good application prospect in bipolar OFETs.
The invention designs and synthesizes a novel fluorine-chlorine substituted cyclized indigo (BAI) receptor and a polymer, and researches the application of the receptor and the polymer in an organic field effect transistor. The polymer has proper HOMO and LUMO energy levels, and test results show that the polymer shows excellent bipolar transmission characteristics. The fluorochlorocycloindigo polymer further expands the types of bipolar materials and has good application prospect in organic optoelectronic devices.
Drawings
FIG. 1 is a scheme showing the synthesis of the polymer of formula I according to example 1 of the present invention.
FIG. 2 is a graph showing the UV-VIS absorption spectrum of a fluorochlorocyclic indigo polymer prepared in example 1 of the present invention.
FIG. 3 is a cyclic voltammogram of a fluorochloro cyclized indigo polymer prepared in example 1 of the present invention.
Fig. 4 is a schematic structural view of a field effect transistor containing a fluorochlorocyclic indigo polymer prepared in example 1 of the present invention.
Fig. 5 is a graph showing an output characteristic and a transfer characteristic of a polymer field effect transistor using a fluorochlorocyclic indigo polymer prepared in example 1 of the present invention as a semiconductor layer.
Detailed Description
The present invention will be described below with reference to specific examples, but the present invention is not limited thereto.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Example 1 preparation of Polymer P2F2ClBAI-V
Preparation of a Polymer of formula I (R is 2-decyltetradecyl; n is 26) according to the synthetic scheme shown in FIG. 1
a) 4-chloro-5-fluoro-2-nitrobenzaldehyde
40g of 4-chloro-3-fluorobenzaldehyde (0.252mol) and 140mL of concentrated sulfuric acid are sequentially added into a round-bottom flask, stirred in an ice bath, and 16mL of concentrated nitric acid is dropwise added. The mixture was stirred at room temperature for 36 hours, and then poured into ice water. Extracting with ethyl acetate, drying, and purifying with column. Eluent (petroleum ether: ethyl acetate ═ 20: 1). Finally, a solid (21.1g, 41.2%) was obtained.
The structural characterization data is as follows:
1H NMR(300MHz,CDCl3)δ10.41(s,1H),8.29(d,J＝6.0Hz,1H),7.75(d,J＝8.1 Hz,1H).13C NMR(100MHz,CDCl3)δ185.7,162.5,159.9,145.3,132.0,132.0,127.9, 127.2,127.0,117.4,117.2.HREI:[M]calcd for C7H3ClFNO3:202.9785,found:202.9786.
b) difluorodichloroindigo (i.e., 2F2Cl-indigo)
20g of 4-chloro-5-fluoro-2-nitrobenzaldehyde (0.098mol),500mL of acetone and 220mL of water were added sequentially to the round-bottom flask and the mixture was sonicated to clear. A2 mol/L aqueous solution of sodium hydroxide (4.72g,0.118mol) was slowly added dropwise with stirring. The mixture was stirred at room temperature for 48 hours. The resulting suspension was filtered, washed with water, ethanol, acetone in that order, and dried to give the product (7.6g, 42.1%).
The structural characterization data is as follows:
the product has poor solubility in common deuterated solvents, so1H NMR and13c NMR was not obtained temporarily. HREI [ M ]] calcd for C16H6Cl2F2N2O2:365.9774,found:365.9770.
c) Dichlorodichlorocycloindigo (i.e., 2F2ClBAI)
Difluorodichloroindigo (6.0g,16.4mmol,1.0equiv) was dissolved in 270mL o-xylene and heated to 140 ℃. To this suspension was added dropwise, under nitrogen, a solution of 2-thiopheneacetyl chloride (10.5g,65.4mmol,4.0equiv) in o-xylene (22 mL). The mixed solution was stirred at 140 ℃ for 24 hours. After cooling, filtration, washing with ethanol, acetone and tetrahydrofuran in this order, the product was obtained after drying (2.2g, 23.3%).
The structural characterization data is as follows:
the product has poor solubility in common deuterated solvents, so1H NMR and13c NMR was not obtained temporarily. HR-MALDI-TOF: [ M + H ]]+calcd for C28H11Cl2F2N2O2S2:578.96071,found:578.95956.
d) Dicycloindigo-dibromo (i.e., 2F2ClBAI-2Br) with difluorodichloro ring
Dichlorodichlorocycloindigo (1.5g,2.59mmol,1.0equiv) was dissolved in 150mL of chloroform, the mixture was ice-cooled, stirred, and N-bromosuccinimide (1.06g,5.95mmol,2.3equiv) was added in portions. The mixture was stirred at room temperature for 12 hours. Adding water for quenching. Filtration, washing with water, ethanol, acetone in that order, and drying gave the product (1.6g, 84.9%).
The structural characterization data is as follows:
the product has poor solubility in common deuterated solvents, so1H NMR and13c NMR was not obtained temporarily. HR-MALDI-TOF: [ M + H ]]+calcd for C28H9Br2Cl2F2N2O2S2:736.77969,found:736.77806.
e) Dichlorodifluorocycloannulated indigo-dithiophene (i.e., 2F2ClBAI-2T)
Under nitrogen, difluorodichlorocyclized indigo-dibromo (1.0g,1.36mmol,1.0equiv), 3- (2-decyltetradecyl) -5-trimethylstannothiophene (1.9g,3.26mmol,2.4equiv), tris (dibenzylideneacetone) dipalladium (298.5mg), and tris (o-tolyl) phosphine (793.8mg) were sequentially added to a two-necked flask. Then 80mL of gas-depleted chlorobenzene and dimethylsulfoxide (3: 1 by volume) were added. The mixture was stirred at 130 ℃ for 24 hours. Cooling to room temperature, removing the solvent by rotary evaporation, and passing through a column. Eluent (petroleum ether: dichloromethane ═ 4: 1). Finally, a blue solid (0.58g, 30.1%) was obtained.
The structural characterization data is as follows:
1H NMR(300MHz,CD2Cl2)δ8.54(d,J＝6.6Hz,2H),8.03(d,J＝9.6Hz,2H),7.62 (d,J＝3.6Hz,2H),7.26(d,J＝3.6Hz,2H),7.17(s,2H),6.91(s,2H),2.56(d,J＝6.9Hz, 4H),1.66(br,2H),1.41–1.02(m,80H),0.87(m,12H).13C NMR(75MHz,CDCl3)δ157.6, 157.1,154.3,144.8,143.4,138.6,136.1,132.8,131.4,126.6,125.1,125.0,124.8,124.5, 124.0,122.6,121.7,121.2,118.8,112.2,111.9,38.9,35.1,33.4,32.0,30.1,29.8,29.7,29.4, 26.7,22.7,14.1.HR-MALDI-TOF:[M]calcd for C84H110Cl2F2N2O2S4:1414.67953,found: 1414.67790.
f) dicycloindigo-dithiophene-dibromine (i.e., 2F2ClBAI-2T-2Br)
Dichlorodifluorocycloannulated indigo-dithiophene (0.4g,0.28mmol,1.0equiv) was dissolved in 25mL of chloroform, the mixture was ice-cooled, stirred, and N-bromosuccinimide (0.116g,0.65mmol,2.3equiv) was added in portions. The mixture was stirred at room temperature for 12 hours. Adding water for quenching. Extracting with chloroform, spin drying, and purifying with column. Eluent (petroleum ether: chloroform: 4: 1). Finally, a blue solid (0.33g, 75.0%) was obtained.
The structural characterization data is as follows:
1H NMR(300MHz,CDCl3)δ8.61(d,J＝6.3Hz,2H),8.05(d,J＝9.3Hz,2H),7.63 (d,J＝3.6Hz,2H),7.22(d,J＝3.6Hz,2H),7.02(s,2H),2.49(d,J＝6.9Hz,4H),1.69(br, 2H),1.38–1.02(m,80H),0.86(m,12H).13C NMR(75MHz,CDCl3)δ157.6,156.7,154.3, 143.8,142.8,138.2,135.8,133.0,131.3,125.9,124.9,124.7,124.7,124.6,124.4,124.4, 123.6,122.6,120.7,118.6,112.2,111.9,110.7,38.6,34.3,33.4,32.0,30.2,29.8,29.7,29.4, 26.6,22.7,14.2.HR-MALDI-TOF:[M]calcd for C84H108Br2Cl2F2N2O2S4:1572.49850, found:1572.49810.
g) polymer P2F2ClBAI-V
Dichlorodifluorocycloindigo-dithiophene-dibromo (88mg,0.056mmol), trans-1, 2-bis (tributyltin) ethylene (33.9mg,0.056mmol), tris (dibenzylideneacetone) dipalladium catalyst (1.97mg), tris (o-tolyl) phosphine ligand (5.24mg), and chlorobenzene (5mL) were added to a reaction flask, oxygen was removed by three freeze-pump-thaw cycles under argon, and the mixture was heated to 130 ℃ for polymerization for 72 hours. After cooling, 5mL of 12mol/L concentrated hydrochloric acid and 100mL of methanol were added, and the mixture was stirred at room temperature for 3 hours and filtered. The obtained precipitate is loaded into a Soxhlet extractor for extraction. Firstly, methanol, acetone and normal hexane are used for extraction until the mixture is colorless, micromolecules and catalysts are removed, and then chloroform is used for extraction to obtain a final product of 62mg, wherein the yield is 72.6%.
The structural characterization data is as follows:
molecular weight: in GPC, Mn is 37.7kDa, Mw is 106.7kDa, PDI is 2.83, and n is 26.
Elemental analysis: anal, calcd, for C86H110Cl2F2N2O2S4:C 71.68,H 7.69,N 1.94；found:C 70.30,H 7.61,N 1.99.
From the above, the compound has a correct structure, and is a compound P2F2ClBAI-V shown in formula I, and the structural formula is shown as follows:
Figure RE-GDA0002503659130000091
wherein R is 2-decyl tetradecyl;
n is 26.
Example 2 spectral, electrochemical and field Effect transistor Performance of Polymer P2F2ClBAI-V
1) Spectral and electrochemical Properties of Polymer P2F2ClBAI-V
FIG. 2 is a graph showing the UV-visible absorption spectra of polymer P2F2ClBAI-V in solution and in film.
As can be seen from FIG. 2, the optical bandgap of the polymer P2F2ClBAI-V is 0.98eV (the optical bandgap is according to the formula E)g1240/λ calculation, where EgIs the optical band gap, and λ is the boundary value of the ultraviolet absorption curve). As can be seen from FIG. 2, the polymer has a strong intramolecular charge transfer peak, indicating that the intermolecular force of the polymer is strong.
FIG. 3 is a cyclic voltammogram of a polymer P2F2ClBAI-V film. The measurements were performed at the electrochemical workstation CHI660c and tested using a conventional three-electrode configuration with platinum as the working electrode, platinum wire as the counter electrode, silver/silver chloride as the reference electrode, and tetrabutylammonium hexafluorophosphate as the supporting electrolyte. The test was performed in acetonitrile solution. The cyclic voltammetry conditions were: the scan range is-1.8 to 1.8 volts (vs. Ag/AgCl) and the scan rate is 50 millivolts per second. The polymer has an oxidation peak and a reduction peak and can be used as a bipolar semiconductor material. According to the cyclic voltammogram, the HOMO and LUMO energy levels of the polymer P2F2ClBAI-V were-5.40 eV and-3.89 eV, respectively. Polymers have suitable HOMO and LUMO energy levels and thus may be ambipolar materials.
2) Field effect transistor performance of polymer P2F2ClBAI-V
Fig. 4 is a schematic structural view of an organic field effect transistor, and as shown in the figure, glass is used as a substrate, and the substrate is subjected to ultrasonic cleaning in secondary water, ethanol and acetone and then is dried in vacuum at 80 ℃. The source and drain electrodes are mask plates, and the gold with the thickness of 25nm is thermally evaporated to be used as the source electrode and the drain electrode. The polymer obtained in example 1 was a semiconductor layer, and an active layer was formed on a glass substrate by a spin coating method using an o-dichlorobenzene solution having a concentration of 10mg/ml, and annealed on a hot stage at 220 ℃ for 10 minutes.
Then, forming 700 nm-thick polymethyl methacrylate on the surface of the polymer film obtained in the embodiment 1 through glue spreading to be used as a dielectric layer of the field effect tube, and removing the solvent for 50 minutes at 90 ℃; and thermally evaporating 90nm thick aluminum on the insulating layer through a mask plate to be used as a gate electrode, and finishing the preparation of the field effect transistor.
The electrical properties of the field effect devices prepared were measured at room temperature with a Keithley 4200SCS semiconductor tester. Two key parameters that determine the performance of OFETs are: carrier mobility (μ) and on-off ratio (I) of the deviceon/Ioff). The mobility refers to the average drift velocity of a carrier (unit is cm) under the action of a unit electric field2 V-1 s-1) Which reflects the mobility of holes or electrons in a semiconductor under an electric field. The on-off ratio is defined as: the ratio of the current in the "on" state and the "off" state of the transistor reflects the performance of the device switch. For a high performance field effect transistor, the mobility and switching ratio should be as high as possible.
Fig. 5 is a transfer characteristic curve and an output characteristic curve of a field effect transistor prepared based on P2F2 ClBAI-V. The polymer field effect transistor shows obvious bipolar transmission characteristics.
The carrier mobility can be calculated from the equation:
IDS＝(W/2L)Ciμ(VG–VT)2(saturation region)
Wherein, IDSIs the drain current, μ is the carrier mobility, VGIs the gate voltage, VTIs the threshold voltage, W is the channel width, L is the channel length, CiIs an insulator capacitor. By means of IDS 1/2To VGPlotting, and performing linear regression to obtain carrier mobility (μ) from the slope of the regression line, and determining V from the intercept of the regression line and the X-axisT。
The mobility can be calculated from the slope of the transfer curve according to the formula, and the device properties of the polymer field effect transistor prepared in each of the above examples are shown in table 1. The switching ratio can be derived from the ratio of the maximum to minimum of the side source-drain currents of fig. 5.
TABLE 1 device Performance of Polymer field Effect transistors
Figure RE-GDA0002503659130000111
Experimental results show that the fluorine-chlorine cyclized indigo polymer is an excellent novel bipolar material. The invention is not limited to the reported materials, a series of polymers can be obtained by changing different side chain substituents, and the synthesis method provided by the invention is simple and effective, and has good guiding significance for synthesizing new bipolar materials.

Claims (10)

1. A polymer of formula I:
Figure RE-FDA0002503659120000011
in the formula I, R is a straight chain or branched chain alkyl with the total number of carbon atoms of 1-40;
ar is the following group:
Figure RE-FDA0002503659120000012
Figure RE-FDA0002503659120000013
represents a substitution bit; n is polymerization degree, and n is 5-100.
2. The polymer of claim 1, wherein: the polymer is represented by the following structural formula:
Figure RE-FDA0002503659120000014
wherein R is 2-decyl tetradecyl;
n is 26.
3. A process for preparing a polymer of formula I according to claim 1, comprising the steps of:
carrying out polymerization reaction on a compound shown as a formula VII and a bistin compound under the action of a catalyst and a ligand to obtain a polymer shown as a formula I;
Figure RE-FDA0002503659120000015
Figure RE-FDA0002503659120000021
in formula VII, R is as defined for R in formula I in claim 1; the bistin compound is as follows:
Figure RE-FDA0002503659120000022
4. the method of claim 3, wherein:
the catalyst is selected from: at least one of tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) palladium dichloride, and tris (dibenzylideneacetone) dipalladium;
the ligand is selected from: at least one of triphenylphosphine, tri (o-tolyl) phosphine, and triphenylarsine;
the feeding molar ratio of the compound shown in the formula VII to the bistin compound, the catalyst and the ligand is 1.0: 0.95-1.05: 0.01-0.10: 0.04 to 0.80.
5. The method according to claim 3 or 4, characterized in that: in the step of polymerization reaction, the temperature is 90-140 ℃; the reaction time is 1 to 80 hours; the polymerization reaction is carried out in a solvent;
the solvent is selected from: at least one of toluene, chlorobenzene, and xylene.
6. A compound of formula VII:
Figure RE-FDA0002503659120000023
in formula VII, R is as defined for R in formula I in claim 1.
7. A process for the preparation of a compound of formula VII as claimed in claim 6, comprising the steps of:
a) carrying out nitration reaction on the 4-chloro-3-fluorobenzaldehyde in a mixed solution of concentrated sulfuric acid and concentrated nitric acid to obtain 4-chloro-5-fluoro-2-nitrobenzaldehyde shown in a formula II;
Figure RE-FDA0002503659120000024
b) reacting the 4-chloro-5-fluoro-2-nitrobenzaldehyde shown in the formula II obtained in the step a), acetone and water in a sodium hydroxide solution to obtain difluorodichloroindigo shown in a formula III;
Figure RE-FDA0002503659120000031
c) carrying out condensation reaction on the difluorodichloroindigo shown in the formula III obtained in the step b) and 2-thiopheneacetyl chloride to obtain difluorodichlorocycloindigo shown in the formula IV;
Figure RE-FDA0002503659120000032
d) brominating the difluorodichlorocyclo-indigo shown in the formula IV obtained in the step c) to obtain difluorodichlorocyclo-indigo-dibromo shown in the formula V;
Figure RE-FDA0002503659120000033
e) performing coupling reaction on the difluorodichlorocyclization indigo-dibromide shown in the formula V obtained in the step d) and a compound a to obtain difluorodichlorocyclization indigo-dithiophene shown in the formula VI;
Figure RE-FDA0002503659120000034
in the compound a, R is defined as the same as R in the formula I in claim 1;
in formula VI, R is as defined for R in formula I in claim 1;
f) brominating difluorodichlorocyclization indigo-dithiophene obtained in the step e) and shown in the formula VI to obtain difluorodichlorocyclization indigo-dithiophene-dibromo shown in the formula VII.
8. Use of a polymer of formula I according to claim 1 or 2 for the preparation of an organic field effect transistor.
9. Use according to claim 8, characterized in that: in said use, the polymers of the formula I according to claim 1 or 2 are used as organic semiconductor layers of organic field-effect transistors;
the organic field effect transistor is a bipolar organic field effect transistor.
10. An organic field effect transistor having as an organic semiconductor layer a polymer of formula I as claimed in claim 1 or 2.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08268974A (en) * 1995-03-28 1996-10-15 Ube Ind Ltd 3-fluoro-4-chloro-6-nitrobenzaldehyde, 3-fluoro-4-chloro-6-nitrobenzaldehyde acetal and their production
US20150303382A1 (en) * 2014-04-17 2015-10-22 The Regents Of The University Of California Bay-Annulated Indigo (BAI) As An Excellent Electron Accepting Building Block for High Performance Organic Semiconductors
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08268974A (en) * 1995-03-28 1996-10-15 Ube Ind Ltd 3-fluoro-4-chloro-6-nitrobenzaldehyde, 3-fluoro-4-chloro-6-nitrobenzaldehyde acetal and their production
US20150303382A1 (en) * 2014-04-17 2015-10-22 The Regents Of The University Of California Bay-Annulated Indigo (BAI) As An Excellent Electron Accepting Building Block for High Performance Organic Semiconductors
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