CN111848649A - Conjugated micromolecule semiconductor material containing halogen modified core group and preparation and application thereof - Google Patents
Conjugated micromolecule semiconductor material containing halogen modified core group and preparation and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of micromolecule donor materials, and particularly discloses a halogen-modified core group-containing conjugated micromolecule semiconductor material, and preparation and application thereof. The micromolecule semiconductor material comprises a halogenated two-dimensional thienothiophene core, a bridging unit and a hexylthiophene end group, and the preparation method is characterized in that an organotin reagent is recycled for reaction and Still coupling is carried out to obtain a target molecule, and the reaction comprises seven steps: the method comprises the following steps of tin reagent reaction, Still coupling reaction, tin reagent reaction, Still unilateral coupling reaction and Still bilateral coupling reaction, wherein in the seven steps of reaction, the three steps of tin reagent reaction are directly carried out on the next step of reaction by using a crude product which does not need to pass through a column, and the method is efficient and simple to operate. The micromolecule semiconductor material has longer ultraviolet-visible absorption range, deeper electron highest occupied orbit and lowest empty orbit, has good solubility and light absorption performance, and can be used as an electron donor material of a micromolecule organic solar cell.
Description
Technical Field
The invention relates to the technical field of organic micromolecule semiconductor materials and organic micromolecule solar cells, in particular to the technical field of micromolecule semiconductor materials, and especially relates to a halogen modified core group-containing conjugated micromolecule semiconductor material and a preparation method thereof.
Background
The organic semiconductor material has rich resources and various and adjustable structures, and is a core material in an organic photovoltaic device. The organic solar cell is one of the most competitive development systems in the third generation of organic solar cells by virtue of the advantages of light weight, flexibility, solution-soluble processing, low cost and large-area printing preparation and the like. Organic solar cells can be classified into polymer organic solar cells and small molecule organic solar cells according to the active layer material of the organic solar cells. For many years, polymer organic solar cells have been the main force for the development of the field, and the maximum photoelectric conversion efficiency of the current solar cells based on polymer donor and small molecule acceptor materials has already broken through 18%. However, the uncertainty and high dispersibility of the molecular weight of the polymer donor material make the purification difficult, and cause batch differences of the material, often cause low repeatability of device efficiency, and become one of the technical barriers for the polymer organic solar cell to move from the laboratory to the practical production and application. And the small-molecule organic solar cell can just make up for the defect. With the increasing requirements of the field on semiconductor materials and the unique advantages of no difference in the accuracy and batch of small molecule material structures, the small molecule material structure becomes one of the hot points of the field development, the efficiency of the small molecule solar cell is broken through in two years, the maximum photoelectric conversion efficiency is broken through by 15% at present, and a good development trend is shown.
The solar cell device taking the small molecule donor material and the small molecule acceptor material as the active layers is called an all-small molecule organic solar cell. The micromolecule receptor material is represented by fullerene and derivatives thereof and non-fullerene fused ring micromolecule receptors, and has long development process. At present, the types of commercially available high-efficiency small-molecule receptor materials are rich, and particularly, non-fullerene fused-ring small-molecule receptor materials are commercially available. The development of the small-molecule donor material is much slower and is impacted by the wave of the development of the polymer solar cell, and the small-molecule donor material has color only in 2006. The preparation method is characterized by comprising an oligothiophene small molecule donor, a one-dimensional thienothiophene (BDT) small molecule donor and a two-dimensional BDT small molecule donor. Particularly, two-dimensional BDT small molecule donor materials have the characteristics of good conjugated pi systems, molecular planarity, high mobility and the like, so that the maximum efficiency record of small molecule solar cells is refreshed almost every year from 2015 to reach 15% of the year. However, efficient small molecule donor materials are still extremely lacking and are always one of the important factors that prevent the efficiency of all small molecule solar cells from being improved.
The application of the halogen modified two-dimensional BDT core unit in a polymer donor material is quite extensive, and recently, a plurality of high-efficiency polymer donor materials containing the halogen modified BDT core, such as D18, PBDB-T-2F (also called PM6), PBDB-T-2Cl and the like, are reported to show excellent molecular planarity and energy level regulation characteristics. However, the structural unit has few reports on application in small-molecule donor materials, and has great development space. In addition, the novel small molecule donor material taking the fluoro-substituted or chloro-substituted two-dimensional BDT as a core unit mainly adopts alkyl chain modified trithiophene as a pi bridge unit, and no molecule adopting rigid bridging units (such as BDD or structurally modified BDD units) as pi bridges is reported. Therefore, the characteristic unit structure is utilized to innovate a pi bridge or an end group unit, a novel micromolecule donor material and a preparation method thereof are developed, a material foundation is laid for the development of micromolecule organic solar cells, and the micromolecule organic solar cell has important research and application values.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a conjugated small molecule semiconductor material containing a halogen modified core group, and a preparation and application thereof, which provides a novel small molecule electron donor material for a small molecule organic solar cell device.
In order to achieve the above objects and other related objects, a first aspect of the present invention provides a conjugated small molecule semiconductor material containing a halogen-modified core group, the small molecule semiconductor material comprising a halogenated two-dimensional thienothiophene core unit, a rigid bridging unit and a hexylthiophene molecular end group, the molecular structural formula of the small molecule semiconductor material is as follows:
in the formula C2H5、C4H9All refer to straight chain alkyl groups and X refers to halogen atoms.
Optionally, in the halogenated two-dimensional thienothiophene (BDT) core unit of the small molecule semiconductor material, the halogen atom is selected from one of fluorine atom (F) and chlorine atom (Cl); the molecular structural formula of the micromolecular semiconductor material is as follows:
in a second aspect, the invention provides a method for preparing a conjugated small molecule semiconductor material containing a halogen modified core group as described in the first aspect, comprising the following steps:
(1) and (3) reaction of a tin reagent: dissolving a raw material A in a dry organic solvent, slowly dripping a hydrogen-pulling reagent while stirring under the protection of inert gas, stirring for reaction, quickly adding a tin reagent, slowly returning to room temperature, stirring overnight, and post-treating a reaction solution after the reaction is finished to obtain a compound I;
(2) still coupling reaction: dissolving a compound I and a raw material B in an organic solvent, adding a catalyst, heating and stirring under the protection of inert gas for reaction, and after the reaction is finished, carrying out post-treatment on a reaction solution to obtain a compound II;
(3) and (3) reaction of a tin reagent: dissolving a compound II in a dry organic solvent F, slowly dripping a hydrogen-withdrawing reagent while stirring under the protection of inert gas, stirring for reaction, quickly adding a tin reagent, slowly returning to room temperature, stirring overnight, and post-treating a reaction solution after the reaction is finished to obtain a compound III;
(4) still coupling reaction: dissolving the compound III and the raw material C in an organic solvent, adding a catalyst, heating and stirring for reaction under the protection of inert gas, and after the reaction is finished, post-treating the reaction solution to obtain a compound IV;
(5) and (3) reaction of a tin reagent: dissolving a compound IV in a dry organic solvent, slowly dripping a hydrogen-pulling reagent while stirring under the protection of inert gas, stirring for reaction, quickly adding a tin reagent, slowly returning to room temperature, stirring overnight, and post-treating a reaction solution after the reaction is finished to obtain a compound V;
(6) still unilateral coupling reaction: dissolving the compound V and the raw material D in an organic solvent, adding a catalyst, heating and stirring for reaction under the protection of inert gas, and after the reaction is finished, carrying out post-treatment on a reaction solution to obtain a compound VI;
(7) still bilateral coupling reaction: dissolving the compound VI and the raw material E in a dry organic solvent, adding a catalyst, heating and stirring under the protection of inert gas for reaction, and after the reaction is finished, carrying out post-treatment on a reaction solution to obtain the micromolecular semiconductor material;
the molecular structural formulas of the compounds I, II, III, IV, V and VI, the raw material A, the raw material B, the raw material C, the raw material D and the raw material E are shown as follows:
wherein, in the molecular structural formula of the raw material E, X refers to halogen atoms.
Further, the halogen atom of the raw material E is selected from one of fluorine atom (F) and chlorine atom (Cl); the raw material E is a compound E-a or E-b, and the molecular structural formulas of the compound E-a and the compound E-b are shown as follows:
further, in the step (2), the mass ratio of the compound I to the raw material B is 1.2:1 to 1:1, preferably 1.1: 1.
In the step (4), the mass ratio of the compound III to the raw material C is 1.2:1 to 1:1, preferably 1: 1.
Further, in the step (6), the mass ratio of the compound V to the raw material D is 0.1:1 to 1:1, preferably 0.5:1, that is, 1: 2.
Further, in the step (7), the mass ratio of the compound VI to the raw material E is 2.5: 1-2: 1, preferably 2.1: 1. Further, in the steps (1), (3) and (5), the organic solvent is any one of anhydrous oxygen-free tetrahydrofuran and N, N-dimethylformamide, the hydrogen extraction reagent is any one of a N-butyl lithium solution and a lithium diisopropylamide solution, and the tin reagent is any one of a trimethyltin chloride solution and a tributyltin chloride solution; preferably, the hydrogen extraction reagent is an n-butyllithium tetrahydrofuran solution, and the tin reagent is a trimethyltin chloride tetrahydrofuran solution.
Further, in the steps (2), (4), (6) and (7), the organic solvent is selected from any one of anhydrous oxygen-free toluene, N-dimethylformamide and dimethyl sulfoxide, the catalyst is a palladium catalyst, and the palladium catalyst is selected from any one of tetratriphenylphosphine palladium, bis (triphenylphosphine) palladium dichloride and bis (dibenzylideneacetone) palladium; preferably, the solvent is anhydrous oxygen-free toluene and the palladium catalyst is palladium tetratriphenylphosphine.
Further, in the steps (1), (3) and (5), the stirring reaction temperature is less than or equal to-78 ℃, and preferably, in the steps (1), (3) and (5), the stirring reaction temperature is-78 ℃.
Further, in the steps (1), (3) and (5), stirring and reacting for 1-1.5 h; preferably, in the steps (1) and (4), the stirring reaction time is 1 h.
Further, in the steps (2), (4), (6) and (7), the heating reaction temperature is 120-135 ℃, preferably 125 ℃.
Further, in the steps (2), (4), (6) and (7), the heating reaction time is 10-48 h; preferably, in the steps (2), (4) and (7), the heating reaction time is 24h, and in the step (6), the heating reaction time is 15 h. Further, in the steps (1) to (7), the inert gas is selected from any one of nitrogen and argon; preferably, the inert gas is nitrogen.
Further, in the steps (1), (3) and (5), the post-treatment method of the reaction solution is separation and purification, and the separation and purification method comprises the following steps: and after the reaction is finished, adding water to stop the reaction, extracting to obtain an upper organic phase and a lower water phase, washing the organic phase with a potassium fluoride saturated solution and water in sequence, collecting the organic phase, drying, filtering and carrying out rotary evaporation to obtain crude products, wherein the crude products are compounds I, III and V. The crude product was used for the next step without further purification.
Further, in the steps (2), (4), (6) and (7), the post-treatment method of the reaction solution is separation and purification, and the separation and purification method comprises the following steps: and after the reaction is finished, stopping heating, cooling the reaction system to room temperature, adding pure water, extracting to obtain a lower organic phase and an upper water phase, washing the organic phases with a saturated potassium fluoride solution and the pure water, combining the organic phases, drying, filtering and carrying out rotary evaporation to obtain a crude product, and carrying out column chromatography separation on the crude product to obtain compounds II, IV and VI and the micromolecular semiconductor material.
Further, in the method for separating and purifying the reaction liquid in the steps (1), (3) and (5), the extraction solvent is selected from any one of ethyl acetate and dichloromethane, and the drying agent is selected from any one of anhydrous magnesium sulfate and anhydrous sodium sulfate; preferably, the extraction solvent is dichloromethane and the drying agent is anhydrous magnesium sulfate.
Further, in the method for separating and purifying the reaction liquid in the steps (2), (4), (6) and (7), the extractant is selected from any one of dichloromethane and trichloromethane, and the drying agent is selected from any one of anhydrous magnesium sulfate and anhydrous sodium sulfate; preferably, the extraction solvent is dichloromethane and the drying agent is anhydrous magnesium sulfate.
Further, in the steps (2), (4), (6) and (7), the column chromatography separation method of the crude product comprises the following steps: and (3) performing silica gel column chromatography on the crude product, adding an eluent to perform column separation, and collecting an effluent component to obtain the product.
Further, in the steps (2) and (4), the eluting agent is petroleum ether; in the steps (6) and (7), the eluting agent is a dichloromethane/petroleum ether mixture, and the volume ratio of dichloromethane to petroleum ether in the dichloromethane/petroleum ether mixture is 1: 4-1.6; preferably the volume ratio of dichloromethane to petroleum ether is 1: 4.
In a third aspect, the invention provides an application of the conjugated small molecule semiconductor material containing the halogen modified core group in the first aspect in preparing a photovoltaic device.
In a fourth aspect, the invention provides a small molecule organic solar cell device comprising the conjugated small molecule semiconductor material according to the first aspect.
As described above, the conjugated small molecule semiconductor material containing halogen modified core group, and the preparation and application thereof of the present invention have the following beneficial effects:
the micromolecule photovoltaic material utilizes halogenated two-dimensional thienothiophene as a core unit, a pi bridge as a rigid bridging unit and hexylthiophene as end groups to jointly construct a novel micromolecule donor material with an A-pi-D-pi-A structure. The reaction raw materials are cheap and easy to obtain, the target product is obtained by the simple organotin reagent reaction and Still coupling reaction cycle repeated operation, the reactions of the three steps of tin reagents in the seven steps of reaction process are directly put into the next step of reaction as crude products, further purification operation is not needed, and the method is efficient and simple to operate; secondly, skillfully synthesizing a compound VI by utilizing a Still unilateral coupling reaction; the mass ratio of the compound V to the raw material D is set to be 1:2, so that the generation of a bilateral product is limited, the reaction time is controlled, the unilateral product is prevented from being converted into a more stable bilateral product, the success of Still unilateral coupling reaction is avoided, and the firmest foundation is laid for the whole synthesis scheme.
In addition, the micromolecular semiconductor material has longer ultraviolet-visible absorption range, good solubility and light absorption performance, and the halogenated core BDT donor unit effectively regulates and controls the molecular energy level, so that the micromolecular semiconductor material has deeper Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO), can be used as an electron donor material of a micromolecular organic solar cell, and has great application potential and value in the field of photovoltaic devices such as organic solar cells.
Drawings
FIG. 1 is a schematic diagram showing a synthetic route of a small molecule semiconductor material 2Cl-BDT-DD in embodiment 1 of the present invention.
FIG. 2 is a diagram showing the UV-VIS spectrum of a small molecule semiconductor material 2Cl-BDT-DD in example 2 of the present invention.
Fig. 3 is a graph showing the results of the electrochemical energy level test in example 3 of the present invention.
FIG. 4 is a schematic diagram showing a synthetic route of a small molecule semiconductor material 2F-BDT-DD in embodiment 4 of the present invention.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
The invention provides a halogen modified core group-containing conjugated micromolecular semiconductor material which can be used as an electron donor material of a micromolecular organic solar cell and has great application potential and value in the field of photovoltaic devices such as organic solar cells and the like.
The preparation method of the conjugated micromolecule semiconductor material containing the halogen modified core group comprises the following steps:
(1) and (3) reaction of a tin reagent: dissolving a raw material A in a dry organic solvent, slowly dripping a hydrogen-pulling reagent while stirring under the protection of inert gas, stirring for reaction, quickly adding a tin reagent, slowly returning to room temperature, stirring overnight, and post-treating a reaction solution after the reaction is finished to obtain a compound I;
(2) still coupling reaction: dissolving a compound I and a raw material B in an organic solvent, adding a catalyst, heating and stirring under the protection of inert gas for reaction, and after the reaction is finished, carrying out post-treatment on a reaction solution to obtain a compound II;
(3) and (3) reaction of a tin reagent: dissolving a compound II in a dry organic solvent F, slowly dripping a hydrogen-withdrawing reagent while stirring under the protection of inert gas, stirring for reaction, quickly adding a tin reagent, slowly returning to room temperature, stirring overnight, and post-treating a reaction solution after the reaction is finished to obtain a compound III;
(4) still coupling reaction: dissolving the compound III and the raw material C in an organic solvent, adding a catalyst, heating and stirring for reaction under the protection of inert gas, and after the reaction is finished, post-treating the reaction solution to obtain a compound IV;
(5) and (3) reaction of a tin reagent: dissolving a compound IV in a dry organic solvent, slowly dripping a hydrogen-pulling reagent while stirring under the protection of inert gas, stirring for reaction, quickly adding a tin reagent, slowly returning to room temperature, stirring overnight, and post-treating a reaction solution after the reaction is finished to obtain a compound V;
(6) still unilateral coupling reaction: dissolving the compound V and the raw material D in an organic solvent, adding a catalyst, heating and stirring for reaction under the protection of inert gas, and after the reaction is finished, carrying out post-treatment on a reaction solution to obtain a compound VI;
(7) still bilateral coupling reaction: dissolving the compound VI and the raw material E in a dry organic solvent, adding a catalyst, heating and stirring for reaction under the protection of inert gas, and after the reaction is finished, post-treating the reaction solution to obtain the micromolecule semiconductor material.
The molecular structural formulas of the compounds I, II, III, IV, V and VI, the raw material A, the raw material B, the raw material C, the raw material D and the raw material E are shown as follows:
wherein, in the molecular structural formula of the raw material E, X refers to halogen atoms.
Specifically, in examples 1 and 4 of the present invention, the starting material E is a compound E-a and E-b, respectively, and the halogen atoms thereof are a fluorine atom (F) and a chlorine atom (Cl), respectively. Of course, the halogen atom of the raw material E may be other halogen atoms such as bromine (Br) and iodine (I) in addition to the fluorine atom (F) and chlorine atom (Cl).
The molecular structural formulas of the compounds E-a and E-b are shown as follows:
in the step (2), the mass ratio of the compound I to the raw material B is controlled to be 1.2: 1-1: 1, and is specifically 1.1:1 in the following examples.
In the step (4), the mass ratio of the compound III to the raw material C is controlled to be 1.2: 1-1: 1, specifically 1:1 in the following examples.
In the step (6), the mass ratio of the compound V to the raw material D should be controlled to be 0.1:1 to 1:1, specifically 0.5:1, i.e. 1:2 in the following examples.
In the step (7), the mass ratio of the compound VI to the raw material E is controlled to be 2.1:1 in the following examples of 2.5: 1-2: 1.
In the steps (1), (3) and (5), the organic solvent is any one of anhydrous oxygen-free tetrahydrofuran and N, N-dimethylformamide, the hydrogen extraction reagent is any one of a N-butyl lithium solution and a lithium diisopropylamide solution, and the tin reagent is any one of a trimethyl tin chloride solution and a tributyl tin chloride solution; in the following examples, the hydrogen-withdrawing reagent was an n-butyllithium tetrahydrofuran solution, and the tin reagent was a trimethyltin chloride tetrahydrofuran solution.
Wherein, in the steps (2), (4), (6) and (7), the organic solvent is selected from any one of anhydrous oxygen-free toluene, N-dimethylformamide and dimethyl sulfoxide, the catalyst is a palladium catalyst, and the palladium catalyst is selected from any one of tetratriphenylphosphine palladium, bis (triphenylphosphine) palladium dichloride and bis (dibenzylideneacetone) palladium; in the following examples, the solvent was anhydrous oxygen-free toluene and the palladium catalyst was palladium tetratriphenylphosphine.
Wherein, in the steps (1), (3) and (5), the stirring reaction temperature is less than or equal to-78 ℃, and in the following examples, the stirring reaction temperature is specifically-78 ℃.
In the steps (1), (3) and (4), the stirring reaction time is controlled to be 1-1.5 h; in the following examples, the stirring reaction time was specifically 1 hour.
In the steps (2), (4), (6) and (7), the heating reaction temperature should be controlled to be 120-135 ℃, and in the following embodiments, the heating reaction temperature is specifically 125 ℃.
Wherein in the steps (2), (4), (6) and (7), the heating reaction time is controlled to be 10-48 h; in the following examples, the heating reaction time in the steps (2), (4) and (7) is specifically 24h, and the heating reaction time in the step (6) is specifically 15 h.
Wherein, in the steps (1) to (7), the inert gas is selected from any one of nitrogen and argon; in the following examples, nitrogen is used as the inert gas.
In the steps (1), (3) and (5), the post-treatment method of the reaction solution is separation and purification, and the separation and purification method comprises the following steps: and after the reaction is finished, adding water to stop the reaction, extracting to obtain an upper organic phase and a lower water phase, washing the organic phase with a potassium fluoride saturated solution and water in sequence, collecting the organic phase, drying, filtering and carrying out rotary evaporation to obtain crude products, wherein the crude products are compounds I, III and V. The crude product was subjected to the next reaction without purification thereof.
In the steps (2), (4), (6) and (7), the post-treatment method of the reaction solution is separation and purification, and the separation and purification method comprises the following steps: and after the reaction is finished, stopping heating, cooling the reaction system to room temperature, adding pure water, extracting to obtain a lower organic phase and an upper water phase, washing the organic phases with a saturated potassium fluoride solution and the pure water, combining the organic phases, drying, filtering and carrying out rotary evaporation to obtain a crude product, and separating the crude product by column chromatography to obtain compounds II, IV and VI and the micromolecular semiconductor material.
In the method for separating and purifying the reaction liquid in the steps (1), (3) and (5), the extractant is selected from any one of ethyl acetate and dichloromethane, and the drying agent is selected from any one of anhydrous magnesium sulfate and anhydrous sodium sulfate; in the following examples, the extraction solvent is specifically dichloromethane, and the drying agent is specifically anhydrous magnesium sulfate.
In the method for separating and purifying the reaction liquid in the steps (2), (4), (6) and (7), the extractant is selected from any one of dichloromethane and trichloromethane, and the drying agent is selected from any one of anhydrous magnesium sulfate and anhydrous sodium sulfate; in the following examples, the extraction solvent is specifically dichloromethane, and the drying agent is specifically anhydrous magnesium sulfate.
In the steps (2), (4), (6) and (7), the column chromatography separation method of the crude product comprises the following steps: and (3) performing silica gel column chromatography on the crude product, adding an eluent to perform column separation, and collecting an effluent component to obtain the product.
Wherein, in the steps (2) and (4), the eluting agent is petroleum ether; in the steps (6) and (7), the eluting agent is a dichloromethane/petroleum ether mixture, and the volume ratio of dichloromethane to petroleum ether in the dichloromethane/petroleum ether mixture is 1: 4-1.6; in the following examples, the volume ratio of dichloromethane to petroleum ether in the dichloromethane/petroleum ether mixture was 1: 4. In the following examples, the starting materials A to E, the catalysts palladium tetrakistriphenylphosphine, tetrahydrofuran (anhydrous and oxygen-free), toluene and the like were purchased from Aldrich, national reagents, Shanghai Tantan technology, Jiangsu Jie A Biotech Co., Ltd.
Example 1
Preparation of 2Cl-BDT-DD
(1) Preparation of Compound I
Raw material A (3.0015g,0.0178mol) was dissolved in dry tetrahydrofuran, stirred at-78 deg.C, and n-butyllithium tetrahydrofuran solution (7.85mL,2.5 mol. L) was slowly added dropwise-1) Stirring at-78 deg.C for 1 hr under nitrogen protection, and rapidly adding trimethyl tin chloride tetrahydrofuran solution (19.6mL,1.0 mol. L)-1) The temperature was slowly returned to room temperature, and the mixture was stirred overnight. After the reaction is finished, addingStopping reaction in water, extracting with ethyl acetate to obtain upper organic phase, washing the organic phase with saturated potassium fluoride solution and water successively, collecting the organic phase, and adding anhydrous MgSO4Drying, filtering and rotary evaporation to remove the solvent from the filtrate to obtain the crude product, i.e. compound I (6.4155g, 98.7%), which can be used for the next reaction without further purification.
(2) Preparation of Compound II
Compound I (2.7412g,8.255mmol) and starting material B (1.8462g,7.504mmol) were dissolved in 50mL of toluene, the oxygen in the solution was purged with nitrogen, and Pd (PPh), a palladium catalyst, was added3)4(0.8670g,0.7503 mmol). The reaction was stirred at 125 ℃ for 24h under nitrogen, cooled to room temperature, poured into 50mL of water and the organic phase separated by extraction with ethyl acetate (analytical grade). The organic phase was washed with saturated potassium fluoride solution and pure water in this order, and then with anhydrous MgSO4(analytical grade) drying. The column was chromatographed on silica gel eluting with petroleum ether to give compound II (2.1451g, 85.8%) as a colorless oil.
Characterization data for compound II are as follows:1H NMR(400MHz,CDCl3)7.12(d,1H,ArH),7.11(d,1H,ArH),6.90(d,1H,ArH),6.71(d,1H,ArH),2.80(t,2H,CH2),2.72(t,2H,CH2),1.72-1.65(m,2H,CH2),1.63-1.58(m,2H,CH2),1.42-1.29(m,12H,CH2),0.88(t,6H,CH3).
(3) preparation of Compound III
Compound II (1.8312g,5.480mol) was dissolved in dry tetrahydrofuran, and a solution of n-butyllithium in tetrahydrofuran (2.4mL,2.5 mol. L) was slowly added dropwise with stirring at-78 deg.C-1) Stirring at-78 deg.C for 1 hr under nitrogen protection, and rapidly adding trimethyl tin chloride tetrahydrofuran solution (6.0mL,1.0 mol. L)-1) The temperature was slowly returned to room temperature, and the mixture was stirred overnight. After the reaction is finished, adding water to stop the reaction, extracting with ethyl acetate to obtain an upper organic phase, washing the organic phase with saturated potassium fluoride solution and water in sequence, collecting the organic phase, and adding anhydrous MgSO4Drying, filtering and rotary evaporation to remove solvent to obtain crude product, i.e. compound III (2.7099g, 100.4%), without further purificationPurifying to obtain the product.
(4) Preparation of Compound IV
Compound III (2.5427g,5.104mmol) and starting material C (0.8264g,5.104mmol) were dissolved in 50mL of toluene, the oxygen in the solution was purged with nitrogen, and Pd (PPh), a palladium catalyst, was added3)4(0.5899g,0.5104 mmol). The reaction was stirred at 125 ℃ for 24h under nitrogen, cooled to room temperature, poured into 50mL of water and the organic phase separated by extraction with ethyl acetate (analytical grade). The organic phase was washed with saturated potassium fluoride solution and pure water in this order, and then with anhydrous MgSO4(analytical grade) drying. The column was chromatographed on silica gel eluting with petroleum ether to give compound IV (0.9394g, 44.7%) as a colorless oil.
Characterization data for compound IV are as follows:1H NMR(400MHz,CDCl3)7.19(d,1H,ArH),7.14(d,1H,ArH),7.01(t,1H,ArH),6.98(s,1H,ArH),6.92(d,1H,ArH),6.72(d,1H,ArH),2.81(t,2H,CH2),2.71(t,2H,CH2),1.73-1.60(m,4H,CH2),1.39-1.36(m,4H,CH2),1.33-1.28(m,8H,CH2),0.90(t,3H,CH3),0.89(t,3H,CH3)。
(5) preparation of Compound V
Compound IV (0.4697g,1.128mol) was dissolved in dry tetrahydrofuran, stirred at-78 deg.C, and n-butyllithium tetrahydrofuran solution (0.47mL,2.5 mol. L) was slowly added dropwise-1) Stirring at-78 deg.C for 1 hr under nitrogen protection, and rapidly adding trimethyl tin chloride tetrahydrofuran solution (1.18mL,1.0 mol. L)-1) The temperature was slowly returned to room temperature, and the mixture was stirred overnight. After the reaction is finished, adding water to stop the reaction, extracting with ethyl acetate to obtain an upper organic phase, washing the organic phase with saturated potassium fluoride solution and water in sequence, collecting the organic phase, and adding anhydrous MgSO4Drying, filtering and rotary evaporation to remove the solvent to obtain the crude product, i.e. compound V (0.6709g, 103.2%), which can be used for the next reaction without further purification.
(6) Preparation of Compound VI
Compound V (0.6568g,1.132mmol) and starting material D (1.3585g,2.264mmol) were dissolved in 25mL of toluene and washed with nitrogenThe gas removes the oxygen in the solution and then the palladium catalyst Pd (PPh) is added3)4(0.1308g,0.1132 mmol). The reaction was stirred at 125 ℃ for 15h under nitrogen, cooled to room temperature, poured into 50mL of water and the organic phase separated by extraction with dichloromethane (analytical grade). Washing the organic phase with saturated potassium fluoride aqueous solution and pure water in sequence, and then using anhydrous MgSO4(analytical grade) drying. Separation by column chromatography on silica gel eluting with dichloromethane/petroleum ether (dichloromethane: petroleum ether: 1:4 by volume) gave compound VI (0.2991g, 29.9%).
Characterization data for compound VI is as follows:1H NMR(400MHz,CDCl3)7.62(d,1H,ArH),7.12(d,1H,ArH),7.11(s,1H,ArH),6.96(d,1H,ArH),6.74(d,1H,ArH),3.40-3.28(m,4H,CH2),2.82(t,2H,CH2),2.74(t,2H,CH2),1.78-1.74(m,2H,CH),1.72-1.63(m,4H,CH2),1.43-1.29(m,28H,CH2),0.96-0.87(m,18H,CH3)。
(7) preparation of Compound 2Cl-BDT-DD
Compound VI (0.0678g,0.0696mmol) and compound E-a (0.1370g,0.1460mmol) were dissolved in 25mL of toluene, the oxygen in the solution was purged with nitrogen, and Pd (PPh), a palladium catalyst, was added3)4(0.0081g,0.0070 mmol). The reaction was stirred at 125 ℃ for 24h under nitrogen, cooled to room temperature, poured into 50mL of water and the organic phase separated by extraction with dichloromethane (analytical grade). Washing the organic phase with saturated potassium fluoride aqueous solution and pure water in sequence, and then using anhydrous MgSO4(analytical grade) drying and removing the solvent to obtain the crude product. Separating by silica gel column chromatography, eluting with dichloromethane/petroleum ether (dichloromethane: petroleum ether ═ 1:4 by volume) to obtain an orange oil, i.e. a compound of formula 2Cl-BDT-DD, and placing in a refrigerator overnight to obtain an orange solid powder (0.1326g, 80.9%) and characterizing data of the compound 2Cl-BDT-DD as follows:1H NMR(400MHz,CDCl3)8.31(s,2H,ArH),7.75(d,2H,ArH),7.41(s,2H,ArH),7.15(d,2H,ArH),7.13(s,2H,ArH),6.96(d,2H,ArH),6.74(d,2H,ArH),3.43(q,2H,CH2),3.35(d,4H,CH2),3.26(q,2H,CH2),2.87(q,8H,CH2),2.74(t,4H,CH2),1.77-1.74(m,6H,CH2),1.72-1.63(m,8H,CH2),1.42-1.32(m,72H,CH2),0.97-0.83(t,48H,CH3)。
example 2
2Cl-BDT-DD ultraviolet-visible absorption Spectrum
The target compounds 2Cl-BDT-DD in the example 1 are respectively prepared into 10-5mol·L-1And 10-2mol·L-1Respectively measuring the ultraviolet absorption of the solution and the film, wherein the film is prepared by using a spin coater at 1200rpm and 10-2mol·L-1The solution is obtained by spin coating on a quartz plate, the scanning range is 200-1100nm, and the measuring instrument is a Perkin Eimer Lambda365 spectrophotometer. The ultraviolet-visible absorption curves of the compound 2Cl-BDT-DD in the chloroform solution and the film are shown in figure 2, and the maximum absorption peaks of the solution are 272nm, 358nm and 492nm respectively; the maximum absorption peaks of the film are respectively 246nm, 384nm and 568 nm. The greater red-shift of the film absorption indicates good stacking and intermolecular forces of the 2Cl-BDT-DD molecules. In addition, the optical band gap of 2Cl-BDT-DD can be estimated to be 1.77eV through the cut-off wavelength in the thin film absorption curve.
Example 3
2Cl-BDT-DD electrochemical energy level analysis
A three-electrode system (a glassy carbon electrode is used as a working electrode, a platinum wire electrode is used as an auxiliary electrode, and an Ag/AgCl glass electrode is used as a reference electrode) is selected, and a cyclic voltammetry characteristic curve of a compound is tested by utilizing an electrochemical workstation. Acetonitrile is used as a solvent to prepare 0.1 mol.L-1Tetrabutylammonium hexafluorophosphate (n-Bu)4NPF6) As an electrolyte solution, 1.0 mg/mL-1Ferrocene solution (Ferrocene, Fc) as standard solution, and oxidation potential E of the standard solution was tested(Fc/Fc+). Dissolving a small amount of 2Cl-BDT-DD in chloroform, transferring the solution to a polished glassy carbon electrode by using a dropper, airing, and testing the oxidation potential of the 2Cl-BDT-DD film; in the same manner, the reduction potential of the 2Cl-BDT-DD film was measured, and the cyclic voltammetry characteristics were shown in FIG. 3. The calculation formula of the electrochemical energy level is as follows: eHOMO＝-[4.8-E(Fc/Fc+)+Eonset OX](eV)，ELUMO＝-[4.8-E(Fc/Fc+)+Eonset RED](eV), respectively by means of the oxidation or reduction cut-off potential (E) in the curveonset OX；Eonset RED) The HOMO and LUMO levels of 2F-BDT-BDD were calculated to be-5.49 eV and-3.72 eV, respectively, and the electrochemical band gaps were further calculated to be 1.77eV, respectively, which correspond to the optical band gap.
At present, the HOMO energy level and the LUMO energy level of a high-efficiency acceptor material are both lower, for an organic solar cell, the absolute value of the difference between the open-circuit voltage and the HOMO energy level of a donor material and the LUMO energy level of the acceptor material is closely related, and 2Cl-BDT-DD has a lower HOMO energy level, can be used as a small-molecule donor material, and is expected to obtain higher open-circuit voltage in a small-molecule device.
Example 4
Preparation of small molecule semiconductor material 2F-BDT-DD
In conclusion, the target compound is obtained by circularly and repeatedly operating the simple organic tin reagent reaction and the Still coupling reaction, and the crude product which does not need column separation is directly put into the next reaction in three steps in the seven-step reaction process, so that the method is efficient, simple to operate and low in material preparation cost; secondly, skillfully synthesizing a compound VI by utilizing a Still unilateral coupling reaction; the mass ratio of the compound V to the raw material D is set to be 1:2, so that the generation of a bilateral product is limited, the reaction time is controlled, the unilateral product is prevented from being converted into a more stable bilateral product, the success of Still unilateral coupling reaction is avoided, and the firmest foundation is laid for the whole synthesis scheme. Optical and electrochemical tests prove that the micromolecule semiconductor material has longer ultraviolet-visible absorption range, good solubility and light absorption performance, and the halogenated core BDT donor unit effectively regulates and controls the molecular energy level, so that the micromolecule semiconductor material has deeper Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO), can be used as an electron donor material of a micromolecule organic solar cell, and has great application potential and value in the field of photovoltaic devices such as organic solar cells.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. The conjugated micromolecule semiconductor material containing the halogen modified core group is characterized by comprising a halogenated two-dimensional thienothiophene core unit, a bridging unit and a hexyl thiophene molecular terminal group, and the molecular structural formula of the micromolecule semiconductor material is as follows:
in the formula C2H5、C4H9All refer to straight chain alkyl groups and X refers to halogen atoms.
2. The small molecule semiconductor material of claim 1, wherein: in a halogenated two-dimensional thienothiophene core unit of the small-molecule semiconductor material, a halogen atom is selected from one of a fluorine atom and a chlorine atom.
3. The method for preparing the conjugated small molecule semiconductor material containing the halogen modified core group according to any one of claims 1 to 2, comprising the steps of:
(1) and (3) reaction of a tin reagent: dissolving a raw material A in a dry organic solvent, slowly dripping a hydrogen-pulling reagent while stirring under the protection of inert gas, stirring for reaction, quickly adding a tin reagent, slowly returning to room temperature, stirring overnight, and post-treating a reaction solution after the reaction is finished to obtain a compound I;
(2) still coupling reaction: dissolving a compound I and a raw material B in an organic solvent, adding a catalyst, heating and stirring under the protection of inert gas for reaction, and after the reaction is finished, carrying out post-treatment on a reaction solution to obtain a compound II;
(3) and (3) reaction of a tin reagent: dissolving a compound II in a dry organic solvent F, slowly dripping a hydrogen-withdrawing reagent while stirring under the protection of inert gas, stirring for reaction, quickly adding a tin reagent, slowly returning to room temperature, stirring overnight, and post-treating a reaction solution after the reaction is finished to obtain a compound III;
(4) still coupling reaction: dissolving the compound III and the raw material C in an organic solvent, adding a catalyst, heating and stirring for reaction under the protection of inert gas, and after the reaction is finished, post-treating the reaction solution to obtain a compound IV;
(5) reaction of three tin reagents: dissolving a compound IV in a dry organic solvent, slowly dripping a hydrogen-pulling reagent while stirring under the protection of inert gas, stirring for reaction, quickly adding a tin reagent, slowly returning to room temperature, stirring overnight, and post-treating a reaction solution after the reaction is finished to obtain a compound V;
(6) still unilateral coupling reaction: dissolving the compound V and the raw material D in an organic solvent, adding a catalyst, heating and stirring for reaction under the protection of inert gas, and after the reaction is finished, carrying out post-treatment on a reaction solution to obtain a compound VI;
(7) still bilateral coupling reaction: dissolving the compound VI and the raw material E in a dry organic solvent, adding a catalyst, heating and stirring under the protection of inert gas for reaction, and after the reaction is finished, carrying out post-treatment on a reaction solution to obtain the micromolecular semiconductor material;
the molecular structural formulas of the compounds I, II, III, IV, V and VI, the raw material A, the raw material B, the raw material C, the raw material D and the raw material E are shown as follows:
wherein, in the molecular structural formula of the raw material E, X refers to halogen atoms.
4. The production method according to claim 3, characterized in that: the halogen atom of the raw material E is selected from one of fluorine atom (F) and chlorine atom (Cl); the raw material E is a compound E-a or E-b, and the molecular structural formulas of the compound E-a and the compound E-b are shown as follows:
5. the production method according to claim 3, characterized in that: in the step (2), the mass ratio of the compound I to the raw material B is 1.2: 1-1: 1;
and/or in the step (4), the mass ratio of the compound III to the raw material C is 1.2: 1-1: 1;
and/or in the step (6), the mass ratio of the compound V to the raw material D is 0.1: 1-1: 1;
and/or in the step (7), the mass ratio of the compound VI to the raw material E is 2.5: 1-2: 1;
and/or in the steps (1), (3) and (5), the organic solvent is any one selected from anhydrous oxygen-free tetrahydrofuran and N, N-dimethylformamide, the hydrogen drawing reagent is any one selected from a N-butyl lithium solution and a lithium diisopropylamide solution, and the tin reagent is any one selected from a trimethyl tin chloride solution and a tributyl tin chloride solution;
and/or in the steps (2), (4), (6) and (7), the organic solvent is selected from any one of anhydrous oxygen-free toluene, N-dimethylformamide and dimethyl sulfoxide, the catalyst is a palladium catalyst, and the palladium catalyst is selected from any one of palladium tetratriphenylphosphine, bis (triphenylphosphine) palladium dichloride and bis (dibenzylideneacetone) palladium;
and/or in the steps (1), (3) and (5), the stirring reaction temperature is less than or equal to-78 ℃;
and/or in the steps (1), (3) and (5), stirring for reaction for 1-1.5 h;
and/or in the steps (2), (4), (6) and (7), the heating reaction temperature is 120-135 ℃, and the heating reaction time is 10-48 h;
and/or, in the steps (1) to (7), the inert gas is selected from any one of nitrogen and argon.
6. The production method according to claim 3, characterized in that: in the steps (1), (3) and (5), the post-treatment method of the reaction solution is separation and purification, and the separation and purification method comprises the following steps: after the reaction is finished, adding water to stop the reaction, extracting to obtain an upper organic phase and a lower water phase, washing the organic phase with a potassium fluoride saturated solution and water in sequence, collecting the organic phase, drying, filtering and carrying out rotary evaporation to obtain crude products, wherein the crude products are compounds I, III and V;
in the steps (2), (4), (6) and (7), the post-treatment method of the reaction solution is separation and purification, and the separation and purification method comprises the following steps: and after the reaction is finished, stopping heating, cooling the reaction system to room temperature, adding pure water, extracting to obtain a lower organic phase and an upper water phase, washing the organic phases with a saturated potassium fluoride solution and the pure water, combining the organic phases, drying, filtering and carrying out rotary evaporation to obtain a crude product, and carrying out column chromatography separation on the crude product to obtain compounds II, IV and VI and the micromolecular semiconductor material.
7. The production method according to claim 3, characterized in that: in the method for separating and purifying the reaction liquid in the steps (1), (3) and (5), the extraction solvent is selected from any one of ethyl acetate and dichloromethane, and the drying agent is selected from any one of anhydrous magnesium sulfate and anhydrous sodium sulfate;
and/or in the method for separating and purifying the reaction liquid in the steps (2), (4), (6) and (7), the extraction solvent is selected from any one of dichloromethane and trichloromethane, and the drying agent is selected from any one of anhydrous magnesium sulfate and anhydrous sodium sulfate;
and/or, in the steps (2), (4), (6) and (7), the column chromatography separation method of the crude product comprises the following steps: and (3) performing silica gel column chromatography on the crude product, adding an eluent to perform column separation, and collecting an effluent component to obtain the product.
8. The method of claim 7, wherein: in the steps (2) and (4), the eluting agent is petroleum ether; in the steps (6) and (7), the eluting agent is a dichloromethane/petroleum ether mixture, and the volume ratio of dichloromethane to petroleum ether in the dichloromethane/petroleum ether mixture is 1: 4-1: 6.
9. Use of the halogen-modified core group-containing conjugated small molecule semiconductor material according to any one of claims 1-2 for the preparation of a photovoltaic device.
10. A small molecule organic solar cell device comprising the conjugated small molecule semiconductor material according to any of claims 1-2.
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