CN111533886A - Donor-receptor type polymer containing fused ring unit based on quinoxalinebenzotriazole and preparation method and application thereof - Google Patents

Donor-receptor type polymer containing fused ring unit based on quinoxalinebenzotriazole and preparation method and application thereof Download PDF

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CN111533886A
CN111533886A CN202010367294.7A CN202010367294A CN111533886A CN 111533886 A CN111533886 A CN 111533886A CN 202010367294 A CN202010367294 A CN 202010367294A CN 111533886 A CN111533886 A CN 111533886A
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ring unit
donor
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应磊
李冠泽
彭沣
曹镛
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South China University of Technology SCUT
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Abstract

The invention discloses a donor-receptor type polymer containing a condensed ring unit based on quinoxalinebenzotriazole, and a preparation method and application thereof. The intermediate, the polymeric monomer and the target polymer semiconductor material have the advantages of short synthetic route steps, high total yield, good repeatability, easiness in amplified synthesis and production and the like. Such polymers also have absorption over a broad spectral range and high electron mobility. The donor-acceptor type polymer based on the quinoxaline benzotriazole-based fused ring unit can be used as an active layer and applied to organic/polymer electronic devices such as organic/polymer photodetectors and organic/polymer solar cells.

Description

Donor-receptor type polymer containing fused ring unit based on quinoxalinebenzotriazole and preparation method and application thereof
Technical Field
The invention belongs to the field of organic photoelectricity, and particularly relates to a donor-receptor type polymer containing a fused ring unit based on quinoxalinebenzenetriazole, and a preparation method and application thereof.
Background
The organic solar cell material starts in the last 90 th century, is a novel sustainable and renewable low-cost green energy material, is easy to prepare large-area flexible cells, and has great application potential. Organic field effect transistors are transistor devices using organic semiconductor materials as active layers, and are drawing attention due to their characteristics of low cost, flexibility, and capability of fabricating large-area devices. Therefore, the attention and investment of a plurality of research institutions and scientific research teams around the world are attracted in the field of organic photovoltaics, and the development of novel efficient and stable materials is the focus of much attention in the field of organic photovoltaics.
The photoelectric detector is a component for converting optical signals into electric signals based on the photoelectric effect, and has important application in the fields of optical communication, image sensing, biomedical sensing, environmental monitoring, meteorology, military and the like. The photodetectors commonly used today are generally based on inorganic semiconductor materials, such as Si-based, Ge-based, and InGaAs, among others.
Compared with inorganic materials, the organic/polymer material has the advantages of low cost, easy adjustment of absorption wavelength, film formation by a solution method, easy adhesion to different substrates and the like, so that organic electronic components such as organic/polymer solar cells, organic/polymer photodetectors and the like have simple manufacturing process, low production cost, light weight, easy large-area preparation, can realize flexible devices and have wide application prospect.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a donor-receptor type polymer containing a fused ring unit based on quinoxalinobenzotriazole, and a preparation method and application thereof. The invention constructs a novel donor-receptor type polymer semiconductor material together with an electron donor unit on the basis of a quinoxaline benzotriazole-based condensed ring unit with strong electric absorbability.
The primary object of the present invention is to provide a novel class of donor-acceptor type polymers consisting of a fused ring unit based on quinoxalinobenzotriazoles and an electron donating unit. The polymer has a narrow band gap and a wide absorption spectrum, and the spectrum is easy to adjust through the structure, so that the polymer can be used for preparing high-efficiency organic/polymer electronic devices, particularly organic/polymer photodetectors and organic/polymer solar cells.
It is another object of the present invention to provide a process for preparing the above donor-acceptor type polymer containing a fused ring unit based on quinoxalinylbenzotriazole.
Still another object of the present invention is to provide use of the above donor-receptor type polymer containing a condensed ring unit based on quinoxalinylbenzotriazole in the field of organic optoelectronics.
The purpose of the invention is realized by at least one of the following technical solutions.
The invention provides a donor-receptor type polymer (D-pi-A type polymer containing a condensed ring unit based on quinoxalinobenzotriazole) containing the condensed ring unit based on the quinoxalinobenzotriazole, and the chemical structural formula of the donor-receptor type polymer meets the following general formula:
Figure BDA0002476943660000021
wherein x and y are mole fractions of each unit, wherein 0< x <1, 0< y <1, and x + y is 1; n is the number of repeating units, n is an integer greater than 1;
R1、R2an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms or an aromatic heterocyclic group having 3 to 60 carbon atoms;
ar is an aromatic hydrocarbon group having 6 to 100 carbon atoms or an aromatic heterocyclic group having 3 to 100 carbon atoms.
Further, the Ar unit is preferably one or more of the following structures or halogenated, deuterated, alkyl-substituted derivatives of the following structures:
Figure BDA0002476943660000022
Figure BDA0002476943660000031
Figure BDA0002476943660000041
wherein R is3Is an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms or an aromatic heterocyclic group having 3 to 60 carbon atoms.
The invention provides a method for preparing the donor-acceptor type polymer containing the fused ring unit based on the quinoxalinylbenzotriazole, which comprises the following steps:
(1) under the protection of inert gas, dissolving an Ar unit monomer containing a dialkyl tin functional group and an A unit monomer of a condensed ring unit based on quinoxalinylbenzotriazole in a solvent, then adding a catalyst to obtain a mixed solution, and heating to perform Stille polymerization reaction to obtain a mixture after polymerization reaction;
(2) after purifying the mixture in the step (1), obtaining the donor-receptor type polymer containing the fused ring unit based on the quinoxalinebenzenetriazole.
Further, the solvent in step (1) includes, but is not limited to, at least one of toluene, tetrahydrofuran, xylene, chlorobenzene, dichlorobenzene, and the like; the catalyst is a Stille polymerization catalyst, and the catalyst comprises at least one of tetrakis (triphenylphosphine) palladium, tris (dibenzylideneacetone) dipalladium/tris (o-methylphenyl phosphine); the A unit monomer of the condensed ring unit based on the quinoxalinobenzotriazole is a double brominated A unit monomer of the condensed ring unit based on the quinoxalinobenzotriazole or a double iodo A unit monomer of the condensed ring unit based on the quinoxalinobenzotriazole; the dosage of the catalyst is 2 per mill-3% of the total mole amount of the reaction monomer; in the mixed solution, the molar amount of the Ar unit monomer containing the dialkyl tin functional group is equal to that of the A unit monomer based on the condensed ring unit of the quinoxalinobenzotriazole; the structural formula of the Ar unit monomer containing the dialkyl tin functional group is one of the following structural formulas:
Figure BDA0002476943660000051
Figure BDA0002476943660000061
wherein R is3Is an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms or an aromatic heterocyclic group having 3 to 60 carbon atoms.
The structural general formula of the A unit monomer of the fused ring unit based on the quinoxalinobenzotriazole is shown as follows:
Figure BDA0002476943660000071
in the formula, R1、R2Each of which is an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms or an aromatic heterocyclic group having 3 to 60 carbon atoms, and X is a bromine atom or an iodine atom.
The amount of the Ar unit monomer containing the double alkyl tin functional group and the A unit monomer of the dibromo or iodo quinoxaline benzotriazole-based fused ring unit is such that the total molar amount of the double alkyl tin functional group-containing monomer is equal to the total molar amount of the double bromine and/or double iodine functional group-containing monomer.
Further, the temperature of the Stille polymerization reaction in the step (1) is 60-180 ℃, and the time of the Stille polymerization reaction is 0.5-72 hours.
Further, the purification of step (2) comprises: and cooling the mixture after the polymerization reaction to room temperature, dropwise adding the mixture into stirred methanol for precipitation, filtering and drying to obtain a crude product, extracting the crude product by using methanol and acetone in sequence, dissolving the crude product by using chlorobenzene, precipitating the crude product in a methanol solution again after concentration, filtering and drying to obtain the target product donor-receptor type polymer containing the fused ring unit based on the quinoxalinobenzo triazole.
Preferably, the present invention provides a method for preparing a donor-receptor type polymer containing a fused ring unit based on quinoxalobenzotriazole, comprising the steps of:
(1) under the protection of inert gas, dissolving an Ar unit monomer containing a dialkyl tin functional group and an A unit monomer of a condensed ring unit based on quinoxalinobenzotriazole in a solvent, and heating for Stille polymerization reaction to obtain a mixture; adding alkyl tin thiophene into the mixture to perform a first heat preservation reaction, then adding bromothiophene to perform a second heat preservation reaction to obtain a reaction solution;
(2) and (2) purifying the reaction solution obtained in the step (1) to obtain the donor-receptor type polymer containing the fused ring unit based on the quinoxalinebenzotriazole.
Furthermore, the usage amount of the alkyl tin thiophene is 10-40% of the total mole amount of the reaction monomers; the dosage of the bromothiophene is 1-20 times of the molar weight of the alkyl tin thiophene; the time of the first heat preservation reaction is 6-12 hours; the time of the second heat preservation reaction is 6-12 hours.
The step of adding alkyltin thiophene and bromothiophene in step (1) and then conducting the incubation reaction is not an essential step and may be omitted if necessary.
The donor-receptor type polymer containing the fused ring unit based on the quinoxalinobenzotriazole provided by the invention can be applied to the preparation of electronic devices. The electronic device comprises more than one of an organic/polymer photoelectric detector, an organic/polymer solar cell, an organic/polymer thin film transistor, an organic/polymer light-emitting transistor, an organic/polymer photoelectric transistor and an organic/polymer organic light-emitting electrochemical cell.
The donor-acceptor type polymer containing the quinoxaline benzotriazole-based fused ring unit provided by the invention can be applied to organic/polymer electronic devices, in particular to organic/polymer photodetectors and organic/polymer solar cells.
The invention provides an application of a donor-receptor type polymer containing a condensed ring unit based on quinoxalinobenzotriazole in preparing an electronic device, which comprises the following steps: dissolving the donor-receptor type polymer containing the quinoxaline benzotriazole-based condensed ring unit or mixing the donor-receptor type polymer with at least one other substance in an organic solvent, and then forming a film through spin coating, ink-jet printing or printing to obtain an active layer of the organic/polymer electronic device; the organic solvent includes but is not limited to more than one of xylene, tetrahydrofuran, chlorobenzene and dichlorobenzene.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) according to the donor-receptor type polymer containing the fused ring unit based on quinoxalino benzotriazole, the D unit and the A unit are directly connected, so that the planarity is strong, and the donor-receptor effect is more remarkable; has wider absorption range and narrower band gap; the solubility is easy to adjust through an alkyl chain connected with benzotriazole and quinoxaline;
(2) the donor-receptor type polymer containing the fused ring unit based on the quinoxalinobenzotriazole provided by the invention has higher electron mobility, and is beneficial to preparing high-efficiency organic electronic devices, in particular organic/polymer batteries and organic/polymer photoelectric detectors;
(3) the quinoxaline benzotriazole-based donor-acceptor compound has the advantages of short preparation route, easily obtained raw materials, simple method, high yield preparation and popularization and application in industrial scale-up synthesis and production.
Drawings
FIG. 1 shows the absorption spectrum of a solid film of polymer P1 on a quartz plate;
FIG. 2 shows the absorption spectrum of a solid film of polymer P3 on a quartz plate;
FIG. 3 shows the solid state thin film absorption spectrum of polymer P6 on a quartz plate and the solution absorption spectrum of polymer P in a quartz cuvette using chloroform as a solvent;
FIG. 4 shows dark current-voltage (J) of a polymer photodetector device based on the polymer P3d-V) a curve;
FIG. 5 shows the detectivity of a polymer photodetector device based on polymer P3 at a bias voltage of-0.1V.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Example 1
Preparation of Compound 7
(1) Preparation of Compound 1
Diazosulfide (6.81g, 50mmol) was dissolved in 200mL concentrated sulfuric acid under nitrogen, and N-bromosuccinimide (18.71g, 105mol) was added in three portions at 60 ℃ and stirred for 12 hours. Pouring the reaction solution into 900mL of ice water, carrying out suction filtration, and washing the filter residue with deionized water, methanol and n-hexane respectively for three times. This operation was repeated 3 times and the last obtained residue was dried to obtain a solid product with a yield of 69%.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
(2) Preparation of Compound 2
Compound 1(5.0g, 17mmol) and reduced iron powder (11.40g, 204mmol) were dissolved in 100mL of anhydrous acetic acid under a nitrogen atmosphere, and the reaction mixture was heated to 150 ℃ and reacted for 3 hours. Cooling, adding diatomite, carrying out suction filtration, adding water and dichloromethane into filtrate obtained by suction filtration, extracting the obtained organic phase layer twice repeatedly by using dichloromethane and water after spin-drying, and obtaining a solid product after spin-drying with the yield of 92%.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
(3) Preparation of Compound 3
Compound 2(4.0g, 15mmol) was dissolved in 100mL of anhydrous acetic acid under nitrogen, sodium nitrite (1.56g, 22.56mmol) was dissolved in 20mL of deionized water, and the solution was gradually dropped through a constant pressure dropping funnelDropwise adding into the reaction system. After all the dropwise addition was completed, the reaction was carried out for 6 hours. And (3) carrying out suction filtration on the reaction solution, washing the filter residue for three times by using deionized water, and drying the obtained filter residue to obtain a solid product with the yield of 77%.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
(4) Preparation of Compound 4
Compound 3(5.54g, 20.0mmol) and potassium carbonate (5.53g, 40.0mmol) were dissolved in 200mL of a mixed solvent of N, N-dimethylformamide with water removed over magnesium sulfate and 5mL of dimethyl sulfoxide under nitrogen protection, the reaction mixture was heated to 80 ℃ for reaction for 1 hour, 2-N-butyl-1-bromooctane (5.98g, 24.0mmol) was added under nitrogen protection, and the reaction mixture was heated to 90 ℃ for reaction for 12 hours. After cooling, the reaction was poured into cold water and the product was extracted with water and dichloromethane and repeated 3 times. Purifying by column chromatography, using 200-300 mesh silica gel as a stationary phase, and using petroleum ether/dichloromethane (4:1) as the polarity of an eluent to obtain a light yellow oily liquid product with the yield of 72%.1H NMR、13The CNMR result shows that the obtained compound is a target product.
(5) Preparation of Compound 5
Under the protection of nitrogen, a mixed acid of concentrated sulfuric acid (40mL) and fuming nitric acid (40mL) is added into a three-neck flask, the three-neck flask is placed in an ice bath condition to be cooled to 0 ℃, and compound 4(4.45g, 10.0mmol) is slowly added into the mixed acid in 4 times at intervals of 10 minutes. After the reaction was carried out for 1 hour in an ice bath, the three-necked flask was transferred to room temperature and the reaction was continued for 6 hours. Pouring the reaction solution into ice water, performing suction filtration, and washing filter residues with water for 3 times. And then purifying by column chromatography, taking 200-300 mesh silica gel as a stationary phase, and using petroleum ether/dichloromethane (2:1) as the polarity of an eluent to obtain a light yellow solid product with the yield of 55%.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
(6) Preparation of Compound 6
Compound 5(1.07g, 2.0mmol) and reduced iron powder (1.34g, 24.0mmol) were dissolved in 100mL of anhydrous acetic acid under nitrogen protection and reacted at 60 ℃ for 4 hours.After cooling, the reaction solution is poured into water, dichloromethane and water are used for extraction for 3 times, then column chromatography is used for purification, silica gel with 200-300 meshes is used as a stationary phase, the polarity of an eluent is petroleum ether/dichloromethane (2:1), and a light gray solid product is obtained, wherein the yield is 91%.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
(7) Preparation of Compound 7
The compound (0.72g, 1.50mmol) was dissolved in 60mL of anhydrous acetic acid under nitrogen protection, and butanedione (274mg, 3.18mmol) was added dropwise to the reaction solution, followed by reaction at 50 ℃ for 12 hours. And (3) cooling, pouring the reaction solution into water, extracting for 3 times by using dichloromethane and water, and purifying by using a column chromatography method, wherein silica gel of 200-300 meshes is used as a stationary phase, and the polarity of an eluent is petroleum ether/dichloromethane (1: 2). Recrystallization from methanol again gave the product as a yellow solid in 81% yield.1HNMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
The chemical reaction equations for synthesizing compounds 1-7 are shown below:
Figure BDA0002476943660000101
Figure BDA0002476943660000111
example 2
Preparation of Compound 11
(1) Preparation of Compound 8
Compound 3 was made according to example 1. Compound 3(5.54g, 20.0mmol) and potassium carbonate (5.53g, 40.0mmol) were dissolved in 180mL of a mixed solvent of N, N-dimethylformamide with water over magnesium sulfate and 5mL of dimethyl sulfoxide under nitrogen protection, the reaction mixture was heated to 85 ℃ for 1 hour, 1-bromohexane (3.32g, 24.0mmol) was added under nitrogen protection, and the reaction mixture was heated to 90 ℃ for 8 hours. After cooling, the reaction was poured into cold water and the product was extracted with water and dichloromethane and repeated 3 times.Purifying by column chromatography, using 200-300 mesh silica gel as a stationary phase, and using petroleum ether/dichloromethane (volume ratio of 4:1) as the polarity of an eluent to obtain a light yellow oily liquid product with the yield of 68%.1H NMR、13The CNMR result shows that the obtained compound is a target product.
(2) Preparation of Compound 9
Triflic acid (37.51g, 250.0mmol) was added to a three-necked flask under nitrogen, the three-necked flask was placed in an ice bath and cooled to 0 ℃ and concentrated sulfuric acid (6.30g, 100.0mmol) was added dropwise. The reaction was cooled in an ice bath for 30 minutes and then brought to room temperature, and the compound (3.61g, 10.0mmol) was added to the reaction at room temperature 6 times with 5-minute intervals. Then, the reaction mixture was heated to 50 ℃ to react for 6 hours. After cooling, the reaction solution was poured into a large amount of ice water, suction filtered, and the filter residue was washed with water 3 times. And then purifying by column chromatography, taking 200-300 mesh silica gel as a stationary phase, and using petroleum ether/dichloromethane (3:2) as the polarity of an eluent to obtain a light yellow solid product with the yield of 47%.1H NMR、13The CNMR result shows that the obtained compound is a target product.
(3) Preparation of Compound 10
Compound 9(2.26g, 5.0mmol) and reduced iron powder (3.36g, 60.1mmol) were dissolved in 200mL of anhydrous acetic acid under nitrogen protection and reacted at 60 ℃ for 4 hours. After cooling, the reaction solution was poured into water, extracted 3 times with dichloromethane and water, and then purified by column chromatography using 200-300 mesh silica gel as the stationary phase and petroleum ether/dichloromethane (3:2) as the polarity of the eluent to give a gray solid product with a yield of 88%.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
(4) Preparation of Compound 11
Compound 10(976mg, 2.5mmol) was dissolved in 120mL of anhydrous ethanol under nitrogen protection, and di (2-thienyl) ethanedione (666mg, 3.0mmol) was added dropwise to the reaction system. Then 10mg of p-toluenesulfonamide was added as a catalyst, and the reaction was carried out under reflux reaction conditions for 12 hours. Cooling, pouring the reaction solution into water, and extracting with dichloromethane and waterAnd 3 times, then purifying by column chromatography, taking 200-300 mesh silica gel as a stationary phase, and using petroleum ether/chloroform (1:1) as a polarity of an eluent. Recrystallization from methanol again gave the product as a yellow solid in 75% yield.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
The chemical reaction equation for synthesizing the compounds 8-11 is shown as follows:
Figure BDA0002476943660000121
Figure BDA0002476943660000131
example 3
Preparation of Compound 12
Compound 10(976mg, 2.5mmol) was dissolved in 120mL of anhydrous acetic acid under nitrogen, and butanedione (451 mg, 5.24 mmol) was added dropwise to the reaction system. The reaction was carried out at 50 ℃ for 12 hours. And (2) cooling, pouring the reaction liquid into water, extracting for 3 times by using dichloromethane and water, and purifying by using a column chromatography method, wherein 200-300-mesh silica gel is used as a stationary phase, and the polarity of an eluent is petroleum ether/dichloromethane (the volume ratio is 2:3), so that a light yellow solid product is finally obtained, and the yield is 78%.1HNMR、13The results of CNMR and element analysis show that the obtained compound is a target product.
Figure BDA0002476943660000132
Example 4
Preparation of Compound 13
Under the protection of nitrogen, thiophene (4.21 g, 50mmol) is dissolved in 250mL of anhydrous tetrahydrofuran, the temperature is reduced to-5 ℃, n-butyllithium (8mL, 200 mmol) is added dropwise, and the mixture is stirred for 2 hours at-5 ℃. A tetrahydrofuran solution of trimethyltin chloride (450mL, 450mmol) was injected, and the reaction was allowed to spontaneously warm to room temperature for 12 hours. After removing tetrahydrofuran by distillation under reduced pressure, the product was extracted with dichloromethane and washed 3 times with deionized waterAfter that, the dichloromethane was spin-dried. Recrystallization from methanol gave the product as a white solid in 86% yield.1HNMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
Figure BDA0002476943660000141
Example 5
Preparation of Compound 15
(1) Preparation of Compound 14
Dithienocyclopentadiene (1.78g, 10mmol), sodium tert-butoxide (2.88g, 30mmol) and bromohexadecane (6.67g, 22mmol) were added to 100mL of tetrahydrofuran under nitrogen atmosphere and ice-bath, and the reaction was stirred for 24 hours. The tetrahydrofuran was spin-dried under reduced pressure, extracted with dichloromethane, washed 3 times with saturated aqueous sodium chloride solution, and the dichloromethane was spin-dried. The crude product is purified by column chromatography by using petroleum ether as eluent to obtain a white solid product with the yield of 90 percent.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
(2) Preparation of Compound 15
Compound 19(3.14g, 5mmol) was dissolved in 150mL of anhydrous tetrahydrofuran under nitrogen, cooled to-5 deg.C, and n-butyllithium (8mL, 20mmol) was added dropwise, and stirred at-5 deg.C for 2 hours. A tetrahydrofuran solution of trimethyltin chloride (45mL, 45mmol) was injected, and the reaction was allowed to spontaneously warm to room temperature for 12 hours. After tetrahydrofuran was distilled off under reduced pressure, the product was extracted with dichloromethane, washed 3 times with deionized water, and dichloromethane was spin-dried. Recrystallization from isopropanol afforded the product as a white solid in 87% yield.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
The chemical reaction equation for synthesizing the compounds 19-20 is as follows:
Figure BDA0002476943660000142
example 6
Preparation of Compound 17
(1) Preparation of Compound 16
Under nitrogen, 3 '-dibromo 2, 2' -bithiophene (3.24g, 10mmol), sodium tert-butoxide (2.40g, 25mmol) 2-octyldodecylamine (3.57g, 12mmol), tris (dibenzylideneacetone) dipalladium (0.46g, 0.5mmol), and 2,2 '-bis- (diphenylphosphino) -1, 1' -binaphthyl (0.62g, 1mmol) were added to 100mL of anhydrous toluene. Heating to 100 deg.C for reaction for 12 hr, washing with saturated sodium chloride water solution for 3 times, spin-drying the solvent in organic layer, and purifying the crude product by column chromatography with petroleum ether as eluent to obtain colorless oily product with a yield of 70%.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
(2) Preparation of Compound 17
The reaction and purification of compound 22 were carried out in analogy to compound 20 to give the product as a pale yellow oil in 84% yield.1HNMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
The chemical reaction equation for synthesizing the compounds 21-22 is shown as follows:
Figure BDA0002476943660000151
example 7
Preparation of Compound 20
(1) Preparation of Compound 18
Thiophene (8.41g, 100mmol) was dissolved in 100mL of anhydrous tetrahydrofuran under nitrogen, cooled to-60 deg.C, n-butyllithium (40mL, 100mmol) was added dropwise, and then stirred at-60 deg.C for 2 hours. Then, bromoisooctane (19.31g, 100mmol) was added to the reaction system, and the reaction was allowed to spontaneously warm to room temperature for 12 hours. After removal of the tetrahydrofuran using a rotary evaporator, the product was extracted with petroleum ether, washed 3 times with deionized water, the dichloromethane was spin-dried and then further purified by distillation under reduced pressure with a yield of 48%.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
(2) Preparation of Compound 19
Under the protection of nitrogen, compound 18(9.82g, 50.0mmol) was dissolved in 150mL of anhydrous tetrahydrofuran, the temperature was reduced to-10 ℃, n-butyllithium (40mL, 100mmol) was added dropwise, the mixture was naturally warmed to room temperature, then heated in an oil bath at 55 ℃, the reaction system was placed in an ice bath for 2 hours after being allowed to react at 55 ℃, and benzo [1,2-b:4,5-b 'was added']Dithiophene-4, 8-dione (3.97g, 18.0mmol) was transferred to room temperature and reacted for 20 minutes, and then tin dichloride (22.0g, 116.1mmol) was dissolved in 25mL of concentrated hydrochloric acid and added to the reaction system. After which it was reacted at room temperature for 12 hours. The reaction solution was poured into ice water, extracted with dichloromethane, washed 3 times with saturated aqueous sodium chloride solution, and dichloromethane was spin-dried. And then purifying by column chromatography, taking 200-300 mesh silica gel as a stationary phase, and using petroleum ether/dichloromethane (9:1) as the polarity of an eluent to finally obtain a yellow solid product with the yield of 66%.1HNMR、13The results of CNMR and element analysis show that the obtained compound is a target product.
(3) Preparation of Compound 20
Compound 19(28.95g, 50.0mmol) was dissolved in 250mL of anhydrous tetrahydrofuran under nitrogen, cooled to-10 ℃ and n-butyllithium (8mL, 20mmol) was added dropwise, followed by stirring at-10 ℃ for 2 hours. A tetrahydrofuran solution of trimethyltin chloride (45mL, 45mmol) was injected, and the reaction was allowed to spontaneously warm to room temperature for 12 hours. After removal of the tetrahydrofuran by rotary evaporator, the product was extracted with dichloromethane, washed 3 times with deionized water and the dichloromethane was spin dried. Recrystallizing with petroleum ether, recrystallizing with anhydrous alcohol, and recrystallizing with anhydrous alcohol to obtain light yellow solid with yield of 75%.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
Figure BDA0002476943660000161
Example 8
Preparation of Polymer P1
Compound 12(88.24mg, 0.2mmol) and compound 19(180.92mg,0.2mmol) were dissolved in 4.4mL of anhydrous chlorobenzene under a nitrogen blanket,tetrakis (triphenylphosphine) palladium (8mg) was added. After 24 hours at 140 ℃ and the first capping with 2- (tributyltin) thiophene (20mg), the reaction was continued for 6 hours after which the second capping with 2-bromothiophene (30mg) was carried out. And (3) finishing the reaction, after the reaction is reduced to room temperature, precipitating the reaction solution in methanol, and extracting the polymer obtained by filtering by using methanol, acetone, normal hexane and chloroform in sequence through a Soxhlet extractor, wherein each extraction lasts for 8 hours. Finally, the solution obtained by chloroform extraction is concentrated, precipitated in methanol, filtered and dried to obtain the fibrous polymer.1The results of H NMR and elemental analysis showed that the obtained compound was the objective product.
The chemical reaction equation for the synthesis of polymer P1 is shown below:
Figure BDA0002476943660000171
example 9
Preparation of Polymer P2
The reaction and purification of polymer P2 were carried out in a similar manner to polymer P1, giving a fibrous polymer.1The results of H NMR and elemental analysis showed that the obtained compound was the objective product. The reaction equation is as follows:
Figure BDA0002476943660000181
example 10
Preparation of Polymer P3
The reaction and purification of polymer P3 were carried out in a similar manner to polymer P1, giving a fibrous polymer.1The results of H NMR and elemental analysis showed that the obtained compound was the objective product.
The reaction equation is as follows:
Figure BDA0002476943660000191
example 11
Preparation of Polymer P4
Under nitrogen protection, compound 12(88.24mg, 0.2mmol) and compound 17(157.09mg,0.2mmol) were dissolved in 4mL of anhydrous o-dichlorobenzene, and tetrakis (triphenylphosphine) palladium (8mg) was added. The reaction was carried out at 140 ℃ for 48 hours, first blocking with 2- (tributyltin) thiophene (20mg) and after 6 hours, second blocking with 2-bromothiophene (30mg) and further reaction was carried out for 6 hours. And (3) finishing the reaction, after the reaction is reduced to room temperature, precipitating the reaction solution in methanol, and extracting the polymer obtained by filtering by using methanol, acetone, normal hexane and chloroform in sequence through a Soxhlet extractor, wherein each extraction lasts for 8 hours. Finally, the solution obtained by chloroform extraction is concentrated, precipitated in methanol, filtered and dried to obtain the fibrous polymer.1The results of H NMR and elemental analysis showed that the obtained compound was the objective product.
The reaction equation is as follows:
Figure BDA0002476943660000201
example 12
Preparation of Polymer P5
Compound 12(88.24mg, 0.2mmol), compound 15(190.57mg,0.2mmol), tris (dibenzylideneacetone) dipalladium (4mg), and tris (o-methylphenyl) phosphorus (8mg) were dissolved in 3.6mL of anhydrous chlorobenzene under a nitrogen atmosphere. The reaction was carried out at 140 ℃ for 48 hours, first blocking was carried out with 2- (tributyltin) thiophene (20mg), after 6 hours, second blocking was carried out with 2-bromothiophene (30mg), and the reaction was continued for 6 hours. And (3) finishing the reaction, precipitating the reaction solution in methanol after the reaction is reduced to room temperature, carrying out Soxhlet extraction on the polymer obtained by filtering by using methanol and acetone successively, carrying out column chromatography by using chloroform as an eluent, and drying to obtain the fibrous polymer.1The results of H NMR and elemental analysis showed that the obtained compound was the objective product.
The chemical reaction equation for the synthesis of polymer P5 is shown below:
Figure BDA0002476943660000202
example 13
Preparation of Polymer P6
The reaction and purification of polymer P6 were carried out in a similar manner to those of polymer P5, and a fibrous polymer was obtained in the same manner.1The results of H NMR and elemental analysis showed that the obtained compound was the objective product.
The reaction equation is as follows:
Figure BDA0002476943660000211
example 14
Measurement of absorption spectra of polymers
FIGS. 1,2 and 3 show UV-VIS-NIR absorption spectra of polymers P1, P3 and P6 on quartz plate or in chlorobenzene solution. As can be seen from FIG. 1, P1 has absorption in a broad wavelength range of 300 to 900 nm. As can be seen from FIG. 2, P3 has absorption in a broad wavelength range of 300 to 1000 nm. As can be seen from FIG. 3, P3 has absorption over a broad wavelength range of 300 to 1200 nm. From these three figures, the polymers P1, P3 and P6 exhibit wide absorption ranges in both solution and film, and the absorption maximum side band values of the film are about 900nm, 1000nm and 1200nm respectively.
Example 15
Preparation of polymer solar cell device
Indium Tin Oxide (ITO) glass with the square resistance of 15 omega, which is prepared in advance, is taken, and ultrasonic cleaning and plasma treatment are sequentially carried out on the Indium Tin Oxide (ITO) glass for 10 minutes by using acetone, a detergent, deionized water and isopropanol. A film of polyethoxythiophene (PEDOT: PSS) doped with polystyrene sulfonic acid was spin-coated on ITO to a thickness of 40 nm. PEDOT PSS films were dried in a nitrogen atmosphere glove box at 80 ℃ for 8 hours. The polymer P1 and PC were then mixed in a mass ratio of 1:1.571A solution of BM in o-dichlorobenzene (1 wt.%) was spin coated on the surface of PEDOT: PSS film to a thickness of 100 nm. Then, a 5nm thick PFN-Br film was spin-coated on the active layer. Finally, a metal Al layer with the thickness of 100nm is evaporated, and the structure of the device is ITO/PEDOT (indium tin oxide)/PSS/P1 (Polybutylece oxide)/PC (polycarbonate)71BM/PFN-Br/Al。
The polymer solar cell based on the polymer P1 as electron donor material possesses a broad absorption from 300nm to 1000nm as shown in fig. 1. The photoelectric conversion efficiency of the device is tested under 1 natural illumination intensity by a standard simulation lamp system, the Photoelectric Conversion Efficiency (PCE) of the device is 5.1 percent, and the device has better photoelectric conversion performance.
Example 16
Preparation of Polymer photodetector
Indium Tin Oxide (ITO) glass with the square resistance of 15 omega, which is prepared in advance, is taken, and ultrasonic cleaning and plasma treatment are sequentially carried out on the Indium Tin Oxide (ITO) glass for 10 minutes by using acetone, a detergent, deionized water and isopropanol. A film of polyethoxythiophene (PEDOT: PSS) doped with polystyrene sulfonic acid was spin-coated on ITO to a thickness of 25 nm. PEDOT PSS films were dried in a nitrogen atmosphere glove box at 80 ℃ for 8 hours. The polymer P3 and PC were then mixed in a mass ratio of 1:1.261A chlorobenzene solution of BM (1 wt.%) was spin coated on the surface of PEDOT: PSS film to a thickness of 100 nm. Then, a 5nm thick PFN-Br film was spin-coated on the active layer. Finally, a metal Al layer with the thickness of 100nm is evaporated, and the structure of the device is ITO/PEDOT (indium tin oxide)/PSS/P3 (Polybutylece oxide)/PC (polycarbonate)61BM/PFN-Br/Al。
The polymer photodetector based on the electron donor material of the polymer P3 has a wide response from 300nm to 1000nm, and as shown in FIG. 2, the current-voltage data of the device is obtained by scanning a current voltage source (Keithley 2400) in a range of-2V to 2V under 850nm illumination, and the dark current J is measured at-0.1VdDown to 2.5 × 10-8A/cm2The detection rate at 850nm wavelength can reach 1.09 × 10, the curve is shown in FIG. 412Jones, can see that the P3-based device has a lower dark current and a higher switching ratio. The curve is shown in fig. 5, and it can be seen that the P3-based device has response in a wide wavelength range and high photodetection rate.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.

Claims (10)

1. A donor-receptor type polymer containing a fused ring unit based on quinoxalinylbenzotriazole is characterized in that the chemical structural formula satisfies the following general formula:
Figure FDA0002476943650000011
wherein x and y are mole fractions of each unit, wherein 0< x <1, 0< y <1, and x + y is 1; n is the number of repeating units, n is an integer greater than 1;
R1、R2an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms or an aromatic heterocyclic group having 3 to 60 carbon atoms;
ar is an aromatic hydrocarbon group having 6 to 100 carbon atoms or an aromatic heterocyclic group having 3 to 100 carbon atoms.
2. The quinoxalinylbenzotriazole-based fused ring unit-containing donor-acceptor type polymer according to claim 1, wherein said Ar unit is preferably one or more of the following structures or a halogenated, deuterated, alkyl-substituted derivative of the following structures:
Figure FDA0002476943650000012
Figure FDA0002476943650000021
Figure FDA0002476943650000031
wherein R is3Is an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms or an aromatic heterocyclic group having 3 to 60 carbon atoms.
3. A method for preparing a donor-receptor type polymer containing a fused ring unit based on quinoxalinylbenzotriazole according to claims 1-2, comprising the steps of:
(1) under the protection of inert gas, dissolving an Ar unit monomer containing a dialkyl tin functional group and an A unit monomer of a condensed ring unit based on quinoxalinylbenzotriazole in a solvent, then adding a catalyst to obtain a mixed solution, and heating to perform Stille polymerization reaction to obtain a mixture after polymerization reaction;
(2) after purifying the mixture in the step (1), obtaining the donor-receptor type polymer containing the fused ring unit based on the quinoxalinebenzenetriazole.
4. The method for producing a donor-acceptor-type polymer containing a condensed ring unit based on quinoxalinylbenzotriazole according to claim 3, wherein the solvent in the step (1) comprises at least one of toluene, tetrahydrofuran, xylene, chlorobenzene, dichlorobenzene; the catalyst is a Stille polymerization catalyst, and the catalyst comprises at least one of tetrakis (triphenylphosphine) palladium, tris (dibenzylideneacetone) dipalladium/tris (o-methylphenyl phosphine); the A unit monomer of the condensed ring unit based on the quinoxalinobenzotriazole is a double brominated A unit monomer of the condensed ring unit based on the quinoxalinobenzotriazole or a double iodo A unit monomer of the condensed ring unit based on the quinoxalinobenzotriazole; the dosage of the catalyst is 2 per mill-3% of the total mole amount of the reaction monomer; in the mixed solution, the molar amount of the Ar unit monomer containing the dialkyl tin functional group is equal to that of the A unit monomer based on the condensed ring unit of the quinoxalinobenzotriazole; the structural formula of the Ar unit monomer containing the dialkyl tin functional group is one of the following structural formulas:
Figure FDA0002476943650000041
Figure FDA0002476943650000051
R3is alkyl with 1-30 carbon atoms, and 3-c30 cycloalkyl groups, aromatic hydrocarbon groups having 6 to 60 carbon atoms, or aromatic heterocyclic groups having 3 to 60 carbon atoms;
the structural general formula of the A unit monomer of the fused ring unit based on the quinoxalinobenzotriazole is shown as follows:
Figure FDA0002476943650000052
in the formula, R1、R2Each of which is an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms or an aromatic heterocyclic group having 3 to 60 carbon atoms, and X is a bromine atom or an iodine atom.
5. The method for preparing a donor-acceptor-type polymer containing a condensed ring unit based on quinoxalinylbenzotriazole according to claim 3, wherein the temperature of the Stille polymerization reaction in the step (1) is 60 to 180 ℃ and the time of the Stille polymerization reaction is 0.5 to 72 hours.
6. The method for producing a donor-receptor-type polymer containing a condensed ring unit based on quinoxalinylbenzotriazole according to claim 3, wherein the purification in step (2) comprises: and cooling the mixture after the polymerization reaction to room temperature, dropwise adding the mixture into stirred methanol for precipitation, filtering and drying to obtain a crude product, extracting the crude product by using methanol and acetone in sequence, dissolving the crude product by using chlorobenzene, precipitating the crude product in a methanol solution again after concentration, filtering and drying to obtain the target product donor-receptor type polymer containing the fused ring unit based on the quinoxalinobenzo triazole.
7. The method for producing a donor-receptor-type polymer containing a condensed ring unit based on quinoxalinylbenzotriazole according to claim 3, characterized by comprising the steps of:
(1) under the protection of inert gas, dissolving an Ar unit monomer containing a dialkyl tin functional group and an A unit monomer of a condensed ring unit based on quinoxalinobenzotriazole in a solvent, and heating for Stille polymerization reaction to obtain a mixture; adding alkyl tin thiophene into the mixture to perform a first heat preservation reaction, then adding bromothiophene to perform a second heat preservation reaction to obtain a reaction solution;
(2) and (2) purifying the reaction solution obtained in the step (1) to obtain the donor-receptor type polymer containing the fused ring unit based on the quinoxalinebenzotriazole.
8. The method for preparing a donor-acceptor-type polymer containing a condensed ring unit based on quinoxalinylbenzotriazole according to claim 7, wherein the alkyl tin thiophene is used in an amount of 10 to 40% of the total molar amount of the reaction monomers; the dosage of the bromothiophene is 1-20 times of the molar weight of the alkyl tin thiophene; the time of the first heat preservation reaction is 6-12 hours; the time of the second heat preservation reaction is 6-12 hours.
9. Use of a quinoxalinylbenzotriazole based fused ring unit containing donor-acceptor type polymer according to any of claims 1-3 for the preparation of an electronic device comprising one or more of an organic/polymer photodetector, an organic/polymer solar cell, an organic/polymer thin film transistor, an organic/polymer light emitting transistor, an organic/polymer phototransistor, an organic/polymer organic light emitting electrochemical cell.
10. Use of a quinoxalinylbenzotriazole based fused ring unit containing donor-acceptor type polymer according to claim 9 for the preparation of electronic devices, characterized in that it comprises: dissolving the donor-receptor type polymer containing the fused ring unit based on the quinoxalinylbenzotriazole in an organic solvent, and then forming a film through spin coating, ink-jet printing or printing to obtain an active layer of the organic/polymer electronic device; the organic solvent comprises more than one of dimethylbenzene, tetrahydrofuran, chlorobenzene and dichlorobenzene.
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