CN110964041A - Receptor material based on benzimide and preparation method and application thereof - Google Patents

Receptor material based on benzimide and preparation method and application thereof Download PDF

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CN110964041A
CN110964041A CN201910460239.XA CN201910460239A CN110964041A CN 110964041 A CN110964041 A CN 110964041A CN 201910460239 A CN201910460239 A CN 201910460239A CN 110964041 A CN110964041 A CN 110964041A
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CN110964041B (en
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黄佳乐
艮文娟
史胜斌
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Shenzhen Ruixun Organic Solar Energy Co Ltd
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Abstract

The invention belongs to the technical field of organic solar cells, and particularly relates to a receptor material based on benzimide. The receptor material based on the benzimide has stronger light absorption in an ultraviolet-visible light region (600-1000nm), has a narrow optical band gap (1.07eV), has a more matched energy level and higher carrier mobility with the existing wide band gap donor material, and is easily soluble in common organic solvents. The short-circuit current can be higher (12.75 mA/cm) when the organic solar cell is applied to the organic solar cell2) And energy conversion efficiency (5.85%), and has wide application prospect.

Description

Receptor material based on benzimide and preparation method and application thereof
Technical Field
The invention belongs to the technical field of organic solar cells, and particularly relates to a receptor material based on benzimide, a preparation method of the receptor material, and application of the receptor material in organic solar cells.
Background
With the increasing severity of energy problems, the development of novel energy is in need, and solar energy has great development prospect due to the advantages of cleanness, no pollution, inexhaustibility, and the like. How to better utilize solar energy is a key solution for dealing with energy crisis. Organic solar cells (OPVs) use organic conjugated molecules as active materials, have many advantages such as light weight, flexibility, wide raw material sources, low cost, solution processibility, large-area fabrication, etc., and have attracted extensive attention in the global academic and industrial fields. The photosensitive active layer material is a host material for converting sunlight into electric energy, is a key factor for determining the performance of the organic solar cell, and generally consists of a donor material and an acceptor material. The development and continuous development progress of conjugated molecular materials are the source power for improving the performance of organic solar cells. In recent years, many kinds of organic conjugated compounds including conjugated polymers, conjugated small molecules, fullerenes, and the like have been widely used in the active layer of a battery, and remarkable results have been obtained. In the development process of organic solar cells, polymer solar cells based on fullerene receptors have excellent performance in terms of receptor materials, and are widely researched and focused by scientists, and fullerene derivatives have been dominating as receptor materials for a long time. However, fullerene derivatives have problems of instability, high cost, weak absorption in a visible light region, difficult energy level regulation, poor polydispersity of molecular weight distribution, poor batch-to-batch repeatability and the like, so that scientists begin to search for photovoltaic materials capable of replacing the fullerene derivatives to adapt to practical production applications.
Organic conjugated molecules have excellent characteristics such as definite molecular structure and molecular weight, anisotropic conjugated skeleton, high purity, batch stability and the like, so that the research on solar cells is more and more popular. Through decades of development, the efficiency of the current organic cell with a single-layer heterojunction breaks through 16%, and the organic cell has the potential of replacing the traditional silicon-based cell in some special fields. However, most of the current acceptor materials commonly used in organic solar cells absorb between 500 nm and 800nm, and the optical band gap (Eg) is wideopt1.55eV), the photoelectric conversion efficiency of the organic solar cell is restricted to some extent, thereby limiting the development of the organic solar cell.
Disclosure of Invention
The invention aims to provide a receptor material based on benzimide, and aims to solve the technical problems of narrow ultraviolet and visible light spectrum absorption band, weak absorption, wide optical band gap and the like of the existing receptor material for an organic solar cell.
Another object of the present invention is to provide a method for preparing a benzimide-based acceptor material.
Another object of the present invention is to provide an organic solar cell.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a benzimide-based receptor material comprising at least one active ingredient of the following compounds of formula (i) and (ii):
Figure BDA0002077821320000021
wherein R is11、R12、R21、R22、R31、R32Are each independently selected from C6～C30An alkyl chain of (a); y is selected from sulfur or selenium; x1And X2Is an electron-withdrawing unit, said X1And X2Each independently selected from any one of the following electron withdrawing groups:
Figure BDA0002077821320000022
wherein R is4Selected from: any one of hydrogen, fluorine, chlorine, cyano, methoxy, sulfoxy and methyl, and T is selected from: any one of oxygen, sulfur and selenium.
A method of preparing a phthalimide-based receptor molecule, comprising the steps of:
obtaining an aldehyde compound and an electron-withdrawing compound based on the benzimide;
obtaining a weakly basic catalyst, dissolving the catalyst, the aldehyde compound based on the benzimide and the electron-withdrawing compound in an organic solvent, and refluxing for 12-24 hours at the temperature of 60-70 ℃ to obtain a receptor molecule based on the benzimide;
wherein the benzimide-based aldehyde compound is selected from the group consisting of:
compound BH
Figure BDA0002077821320000031
Or compound NH
Figure BDA0002077821320000032
The electron-withdrawing compound is selected from any one of the following compounds:
Figure BDA0002077821320000033
wherein R is1、R2、R3Are each independently selected from C6～C30Y is selected from sulfur or selenium, R4Selected from: any one of hydrogen, fluorine, chlorine, cyano, methoxy, sulfoxy and methyl, and T is selected from: any one of oxygen, sulfur and selenium.
An organic solar cell comprising a light trapping active layer comprising the above-described phthalimide-based acceptor material or the above-described phthalimide-based acceptor molecule prepared by the above-described method.
The invention provides a receptor material based on benzimide, which comprises an active component of a benzimide polycyclic receptor molecule, wherein the active component takes a unit containing the benzimide or the dibenzoimide as an electron-donating unit D, takes a unit rich in cyano and ketone groups as an electron-withdrawing unit A, and is simultaneously connected with the electron-withdrawing unit A at two ends of the central electron-donating unit D to form the benzimide polycyclic receptor micromolecule with an A-D-A conjugated structure. In one aspect, containing a benzimide or a bisbenzeneThe electron-donating unit of the polyimide unit is an intermediate core with a D-A-D structure, and the benzimide or the bisbenzimide in the intermediate core can adjust the electron-withdrawing capability of the small molecule and adjust and control the energy level of the small molecule acceptor. On the other hand, the electron-withdrawing unit A is rich in cyano and ketone groups, has strong electron-withdrawing capability, and can accurately regulate and control the energy level of the small molecule acceptor together with the electron-donating unit. The acceptor micromolecules with the A-D-A conjugated structure, which are composed of the electron donating units and the electron withdrawing units, increase the charge transfer efficiency in molecules, improve the carrier mobility, reduce the optical band gap of the acceptor micromolecules and improve the photoelectric conversion efficiency of the organic solar cell. In addition, at least 5 branched alkyl groups with 6-30 carbon atoms are introduced to the side of the electron donor unit, so that the flatness of the central core fused ring unit can be improved, the charge mobility is improved, the pi-pi accumulation among molecules is enhanced, the LUMO energy level of the material is reduced, the space twist of the A-D-A receptor small molecular structure is increased, the molecular solubility is improved, and the intermolecular aggregation is reduced. The receptor material based on the benzimide has a wide absorption band (350nm-1200nm), has strong light absorption in an ultraviolet-visible light region (600-1000nm), has a narrow optical band gap (1.07eV), has a better matched energy level and higher carrier mobility with the existing donor material with a wide band gap, and is easy to dissolve in common organic solvents. The short-circuit current can be higher (12.75 mA/cm) when the organic solar cell is applied to the organic solar cell2) And energy conversion efficiency (5.85%), and has wide application prospect.
According to the preparation method of the receptor molecule based on the benzimide, under the action of a weakly alkaline catalyst, an electron-withdrawing compound with active methylene is connected to two ends of an aldehyde compound based on the benzimide through a Knoevenagel condensation reaction to form the receptor molecule with an A-D-A conjugated structure. The preparation method of the receptor molecule based on the benzimide provided by the invention has the advantages of mild conditions, simple and convenient operation, low preparation cost and high yield, and is beneficial to large-scale production and application. The receptor molecule based on the benzimide prepared by the embodiment of the invention has stronger light absorption in an ultraviolet-visible light region (600-1000nm), higher photoelectric conversion efficiency (PCE > 5%), more matched energy level and higher carrier mobility with the existing wide band gap donor material, can be used for preparing organic solar cells with high current, high voltage and high energy conversion efficiency, has better solubility and is easily soluble in common organic solvents such as chloroform, chlorobenzene, toluene, xylene and the like.
The organic solar cell provided by the invention takes the above-mentioned benzimidazole-based acceptor material or the benzimidazole-based acceptor molecule prepared by the above-mentioned method as an active component in the active layer for light capture, the active component has the absorption bandwidth of ultraviolet visible light spectrum (350-1200nm), has strong light absorption in an ultraviolet-visible light region (600- & ltSUB & gt- & gt 1000nm), narrow optical band gap, strong light absorption capacity, good sunlight capturing capacity, good solubility and other excellent performances, is applied to an active layer for light capturing of an organic solar cell device, has more matched energy level and higher carrier mobility with the existing wide-bandgap donor material, can be used for preparing organic solar cells with high current, high voltage and high energy conversion efficiency, and enables devices to have higher short-circuit current (12.75 mA/cm).2) The high open-circuit voltage (0.79V) and the high photoelectric conversion efficiency (up to 5.85 percent) have wide application prospect.
Drawings
FIG. 1 is a schematic diagram of the synthetic route for the phthalimide-based acceptor molecule (BH-CN) provided in example 1 of the present invention.
FIG. 2 is a schematic diagram of the synthetic route of the phthalimide-based receptor molecule (NH-CN) provided in example 2 of the present invention.
FIG. 3 is an absorption spectrum of a benzimide-based acceptor molecule (BH-CN) provided in example 1 of the present invention in a chloroform solution and in a thin film state.
FIG. 4 is an absorption spectrum of a benzimide-based receptor molecule (NH-CN) provided in example 2 of the present invention in a chloroform solution and in a thin film state.
FIG. 5 is a plot of cyclic voltammograms of a phthalimide-based acceptor molecule (BH-CN) as provided in example 1 of the present invention.
FIG. 6 is a plot of cyclic voltammograms of a benzimide-based acceptor molecule (NH-CN) provided in example 2 of the present invention.
FIG. 7 is a current-voltage (J-V) graph of an organic solar cell of example 3 of the present invention providing a benzimide-based acceptor molecule BH-CN.
FIG. 8 is a current-voltage (J-V) graph of an organic solar cell of example 4 of the present invention providing a benzimide-based acceptor molecule NH-CN.
Detailed Description
In order to make the purpose, technical solution and technical effect of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention is clearly and completely described, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive step in connection with the embodiments of the present invention shall fall within the scope of protection of the present invention.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The weight of the related components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present invention as long as it is in accordance with the description of the embodiments of the present invention. Specifically, the weight described in the description of the embodiment of the present invention may be a unit of mass known in the chemical industry field, such as μ g, mg, g, and kg.
In the present invention,
Figure BDA0002077821320000051
etc. in the structures with a connecting bond, the connecting sites are indicated.
The embodiment of the invention provides a receptor material based on benzimide, which at least comprises one active ingredient of the following compounds in formula (I) and formula (II):
Figure BDA0002077821320000061
wherein R is11、R12、R21、R22、R31、R32Are each independently selected from C6～C30An alkyl chain of (a); y is selected from sulfur or selenium; x1And X2Is an electron-withdrawing unit, said X1And X2Each independently selected from any one of the following electron withdrawing groups:
Figure BDA0002077821320000062
wherein R is4Selected from: any one of hydrogen, fluorine, chlorine, cyano, methoxy, sulfoxy and methyl, and T is selected from: any one of oxygen, sulfur and selenium.
The receptor material based on the benzimide provided by the embodiment of the invention comprises an active component of a benzimide polycyclic receptor molecule, wherein the active component takes a unit containing the benzimide or the dibenzoimide as an electron-donating unit D, a unit rich in cyano and ketone groups as an electron-withdrawing unit A, and the two ends of the central electron-donating unit D are simultaneously connected with the electron-withdrawing unit A to form the benzimide polycyclic receptor micromolecule with an A-D-A conjugated structure. On one hand, the electron-donating unit containing the benzimide or the bisbenzimide unit is an intermediate core with a D-A-D structure, and the benzimide or the bisbenzimide in the intermediate core can adjust the electron-withdrawing capability of the small molecule and regulate the energy level of the small molecule acceptor. On the other hand, the electron-withdrawing unit A is rich in cyano group and ketone group, has a strong electron-withdrawing ability, and together with the electron-donating unit, can be made preciseRegulating and controlling the energy level of the small molecule receptor. The acceptor micromolecules with the A-D-A conjugated structure, which are composed of the electron donating units and the electron withdrawing units, increase the charge transfer efficiency in molecules, improve the carrier mobility, reduce the optical band gap of the acceptor micromolecules and improve the photoelectric conversion efficiency of the organic solar cell. In addition, at least 5 branched alkyl groups with 6-30 carbon atoms are introduced to the side of the electron donor unit, so that the flatness of the central core fused ring unit can be improved, the charge mobility is improved, the pi-pi accumulation among molecules is enhanced, the LUMO energy level of the material is reduced, the space twist of the A-D-A receptor small molecular structure is increased, the molecular solubility is improved, and the intermolecular aggregation is reduced. The receptor material based on the benzimide provided by the embodiment of the invention has a wide absorption band (350nm-1200nm), has strong light absorption in an ultraviolet-visible light region (600-1000nm), has a narrow optical band gap (1.07eV), has a more matched energy level and higher carrier mobility with the existing donor material with the wide band gap, and is easily soluble in common organic solvents. The short-circuit current can be higher (12.75 mA/cm) when the organic solar cell is applied to the organic solar cell2) And energy conversion efficiency (5.85%), and has wide application prospect.
Specifically, the electron donating unit of the active ingredient in the benzimide-based acceptor material provided by the embodiment of the invention is a multi-ring structure containing a benzimide or a bisbenzimide unit:
Figure BDA0002077821320000071
or
Figure BDA0002077821320000072
Wherein R is11、R12、R21、R22、R31、R32The carbon atoms are 6-30 alkyl chains, and Y is sulfur or selenium. The electron donor unit of the embodiment of the invention is a D-A-D conjugated structure consisting of a benzimide or a bisbenzimide middle nuclear electron-deficient acceptor and an electron-rich donor unit connected to two sides of the benzimide middle nuclear electron-deficient acceptor and containing an alkyl chain thienothiophene unit, and the conjugated structure is characterized in thatThe structural coplanarity degree is higher, and the interaction between the donor unit and the acceptor unit in the acceptor micromolecule can be effectively increased. In addition, the nitrogen atoms in the electron donor units are not only used as coplanar heteroatom bridges, but also provide conditions for introducing side alkyl branched chains, so that the space twist of the acceptor micromolecules is increased, the solubility of the acceptor molecules is improved, and the aggregation among the molecules is reduced. In addition, sulfur and selenium elements in the polycyclic electron donor unit can also play a role in adjusting the ultraviolet absorption, intermolecular accumulation, optical band gap and other properties of acceptor molecules.
As a preferred embodiment, said C6～C30The alkyl chain of (a) is:
Figure BDA0002077821320000073
Figure BDA0002077821320000074
any one of them. Inventive example C6～C30The alkyl chain is a branched alkyl group or a straight alkyl group with 6-30 carbon atoms, wherein a branched chain is formed on a second carbon atom close to the N atom, and the branched alkyl group or the straight alkyl group is introduced into the receptor molecule, so that the flatness of a multi-ring structure containing a benzimide or a bisbenzimide unit is improved, the charge mobility is improved, the space twist of an A-D-A conjugated receptor molecule is increased, the solubility of the receptor molecule is effectively improved, and the aggregation among molecules is reduced.
Specifically, the electron-withdrawing unit of the active ingredient in the phthalimide-based acceptor material provided by the embodiment of the invention is an electron-withdrawing group which is rich in cyano and ketone groups and has strong electron-withdrawing capability:
Figure BDA0002077821320000081
wherein R is4Selected from: any one of hydrogen, fluorine, chlorine, cyano, methoxy, sulfoxy and methylIn one embodiment, T is selected from: any one of oxygen, sulfur and selenium. The electron-withdrawing group contains a cyano group and a ketone group, wherein the cyano group has strong electron-withdrawing capability, so that acceptor micromolecules have lower energy level, better light absorption and narrower optical band gap; the ketone group can reduce the energy level of the material, so that the obtained molecules have better electron mobility and proper optical absorption. In addition, the substituent such as halogen, methoxy, sulfoxy and the like contained in the electron-withdrawing unit can further increase the electron-withdrawing capability of the group, thereby enhancing the electron transfer efficiency in acceptor molecules.
In some embodiments, an electron withdrawing group
Figure BDA0002077821320000082
Can be
Figure BDA0002077821320000083
And/or
Figure BDA0002077821320000084
In some embodiments, an electron withdrawing group
Figure BDA0002077821320000085
Can be
Figure BDA0002077821320000086
And/or
Figure BDA0002077821320000087
In some embodiments, an electron withdrawing group
Figure BDA0002077821320000088
Can be
Figure BDA0002077821320000089
And/or
Figure BDA00020778213200000810
In some embodiments of the present invention, the,the electron withdrawing unit of the active ingredient in the phthalimide-based acceptor material is selected from:
Figure BDA00020778213200000811
or
Figure BDA00020778213200000812
The electron-withdrawing unit contains halogen, methoxy, cyano and keto, so that the electron-withdrawing capability of the acceptor unit can be effectively improved, the acceptor micromolecule has lower energy level, better light absorption and narrower optical band gap, the energy level of the material is reduced, and the obtained molecule has better electron mobility.
As a preferred embodiment, said R11And R12Selected from the same said C6～C30Said R is21And R22Selected from the same said C6～C30Said R is31And R32Selected from the same said C6～C30Alkyl chain of (a), said X1And X2Selected from the same said electron withdrawing groups. The active ingredients of the receptor material based on the benzimide are organic conjugated molecules with symmetrical structures, so that the synthetic efficiency is higher, and the preparation process is simpler.
In some embodiments, the active ingredient of the phthalimide-based receptor material has a structural formula:
Figure BDA0002077821320000091
or
Figure BDA0002077821320000092
In some embodiments, the active ingredient of the phthalimide-based receptor material has a structural formula:
Figure BDA0002077821320000093
or
Figure BDA0002077821320000094
In some embodiments, the active ingredient of the phthalimide-based receptor material has a structural formula:
Figure BDA0002077821320000095
or
Figure BDA0002077821320000096
In some embodiments, the active ingredient of the phthalimide-based receptor material has a structural formula:
Figure BDA0002077821320000101
or
Figure BDA0002077821320000102
The embodiment of the invention also provides a preparation method of the receptor molecule based on the benzimide, which comprises the following steps:
s10, obtaining an aldehyde compound and an electron-withdrawing compound based on the benzimide;
s20, obtaining a weakly basic catalyst, dissolving the catalyst, the aldehyde compound based on the benzimide and the electron-withdrawing compound in an organic solvent, and refluxing for 12-24 hours at the temperature of 60-70 ℃ to obtain receptor molecules based on the benzimide;
wherein the benzimide-based aldehyde compound is selected from the group consisting of:
compound BH
Figure BDA0002077821320000103
Or compound NH
Figure BDA0002077821320000104
The electron-withdrawing compound is selected from any one of the following compounds:
Figure BDA0002077821320000105
wherein R is1、R2、R3Are each independently selected from C6～C30Y is selected from sulfur or selenium, R4Selected from: any one of hydrogen, fluorine, chlorine, cyano, methoxy, sulfoxy and methyl, and T is selected from: any one of oxygen, sulfur and selenium.
According to the preparation method of the receptor molecule based on the benzimide, provided by the embodiment of the invention, under the action of a weakly basic catalyst, an electron-withdrawing compound with active methylene is connected to two ends of an aldehyde compound based on the benzimide through a Knoevenagel condensation reaction to form the receptor molecule with an A-D-A conjugated structure. The preparation method of the receptor molecule based on the benzimide provided by the embodiment of the invention has the advantages of mild conditions, simple and convenient operation, low preparation cost and high yield, and is beneficial to large-scale production and application. The receptor molecule based on the benzimide prepared by the embodiment of the invention has stronger light absorption in an ultraviolet-visible light region (600-1000nm), higher photoelectric conversion efficiency (PCE > 5%), better matched energy level and higher carrier mobility with the existing wide band gap donor material, can be used for preparing organic solar cells with high current, high voltage and high energy conversion efficiency, has better solubility, is easy to dissolve in common organic solvents such as chloroform, chlorobenzene, toluene, xylene and the like, and has wide application prospect.
Specifically, in the above step S10, the aldehyde-based compound and the electron-withdrawing compound based on the benzimide are obtained. Wherein the aldehyde-based compound is selected from the group consisting of:
compound BH
Figure BDA0002077821320000111
Or compound NH
Figure BDA0002077821320000112
The electron-withdrawing compound is selected from any one of the following compounds:
Figure BDA0002077821320000113
wherein R is1、R2、R3Are each independently selected from C6～C30Alkyl chain of (A), R4Selected from: any one of hydrogen, fluorine, chlorine, cyano, methoxy, sulfoxy and methyl, Y is selected from any one of sulfur and selenium, T is selected from: any one of oxygen, sulfur and selenium. In the embodiment of the invention, an aldehyde compound based on benzimide and an electron-withdrawing compound containing a cyano group and a ketone group and having strong electron-withdrawing capability are used as raw materials to synthesize an acceptor molecule with an A-D-A conjugated structure, wherein the characteristics and advantages of an electron-withdrawing group and an electron-donating group are discussed in the foregoing and are not repeated here.
In some embodiments, the C6～C30The alkyl chain of (a) is:
Figure BDA0002077821320000121
Figure BDA0002077821320000122
any one of them.
Specifically, in step S20, a weakly basic catalyst is obtained, and the catalyst, the aldehyde-based compound based on the benzimide, and the electron-withdrawing compound are dissolved in an organic solvent and refluxed at 60 to 70 ℃ for 12 to 24 hours to obtain the receptor molecule based on the benzimide. According to the embodiment of the invention, the aldehyde compound and the electron-withdrawing compound are dissolved in an organic solvent, reflux is carried out for 12-24 hours at the temperature of 60-70 ℃, the aldehyde compound and the electron-withdrawing compound based on the benzimide are subjected to a Knoevenagel condensation reaction under the action of a weakly alkaline catalyst, and the electron-withdrawing group is connected to two ends of an electron-donating unit based on the benzimide to form an A-D-A conjugated acceptor molecule based on the benzimide. The preparation method is simple, mild in condition and high in yield.
As a preferred example, the molar ratio of the benzimide-based aldehyde-based compound and the electron-withdrawing compound is 1: (8-20). The embodiment of the invention adopts the following components in a molar ratio of 1: the aldehyde compound and the electron-withdrawing compound in the reaction ratio of (8-20) are used, so that the Knoevenagel condensation reaction between the aldehyde compound based on the benzimide and the electron-withdrawing compound containing the active methylene is more complete, and the preparation efficiency and yield of the receptor molecule based on the benzimide are further ensured.
As a preferred embodiment, the weakly basic catalyst is selected from: piperidine, pyridine or quinoline. The piperidine, pyridine or quinoline catalyst selected by the embodiment of the invention has high catalytic efficiency, and can effectively catalyze the Knoevenagel condensation reaction between the aldehyde compound based on the benzimide and the electron-withdrawing compound containing the active methylene to obtain the receptor molecule with an A-D-A conjugated structure. As a more preferred embodiment, the weakly basic catalyst is selected from pyridine.
As a preferred embodiment, the organic solvent is selected from: chloroform or dichloromethane. The chloroform or dichloromethane organic solvent used in the embodiment of the invention has a good dissolving effect on the aldehyde compound based on the benzimide and the electron-withdrawing compound containing the active methylene, so that the raw material compounds are fully dissolved, the full contact reaction between the raw material compounds in the condensation reaction process is facilitated, the reaction efficiency is improved, and the synthesis yield of the receptor molecule with the A-D-A conjugated structure is improved.
In some embodiments, the method of preparing the phthalimide-based receptor molecule is: and dissolving a pyridine catalyst, the aldehyde compound and the electron-withdrawing compound in a chloroform solvent, and refluxing for 12-24 hours at the temperature of 60-70 ℃ to obtain the receptor molecule based on the benzimide.
As a preferred embodiment, the preparation of the benzimide-based aldehyde-based compound comprises the steps of:
s11, obtaining a 4, 7-dibromo-benzimide compound A, and carrying out nitration reaction under the conditions of concentrated sulfuric acid and fuming nitric acid to obtain a compound B;
s12, obtaining a compound C, and carrying out Stille coupling reaction on the compound B and the compound C under the catalysis condition of bis (triphenylphosphine) palladium dichloride or tetrakis (triphenylphosphine) palladium to obtain a compound D;
s13, carrying out condensation ring-closing reaction on the compound D under the catalysis of triethyl phosphite to obtain a compound E;
s14, obtaining bromoalkane, and carrying out nucleophilic substitution reaction on the compound E and the bromoalkane under the conditions that a solvent is N, N-dimethylformamide and a neutralizing agent is potassium hydroxide to obtain a compound F;
s15, carrying out Vilsmeier-Haack reaction on the compound F under the condition of phosphorus oxychloride to obtain an aldehyde compound based on the benzimide.
Wherein the 4, 7-dibromo-benzimidazole compound A is selected from the following compounds:
Figure BDA0002077821320000131
or
Figure BDA0002077821320000132
The compound C is
Figure BDA0002077821320000133
Wherein Y is selected from sulfur or selenium; the brominated alkanes are selected from: c6～C30To (3) a brominated alkane.
According to the preparation method of the aldehyde compound based on the benzimide, 4, 7-dibromo-benzimide compound A is used as a raw material, and the aldehyde compound based on the benzimide can be obtained through the steps of Stille coupling reaction, condensation ring-closing reaction, nucleophilic substitution reaction, Vilsmeier-Haack reaction and the like. The preparation method has the advantages of simple operation, high flexibility, clear synthetic route and high synthetic efficiency.
Specifically, in step S11, 4, 7-dibromo-benzimide compound a is obtained, and a nitration reaction is performed under the conditions of concentrated sulfuric acid and fuming nitric acid to obtain compound B. As a preferred embodiment, the step of the nitration reaction comprises: according to the volume ratio of the concentrated sulfuric acid to the fuming nitric acid being 1: (1-3) mixing the concentrated sulfuric acid and the fuming nitric acid to obtain a nitration reagent; and carrying out nitration reaction on the 4, 7-dibromo-phthalimide compound A in the nitration reagent for 8-24 hours at the temperature of 80-100 ℃ to obtain a compound B. More preferably, the mass ratio of the compound a to the nitrating agent is 1: (10-30).
When the 4, 7-dibromo-benzimidazole compound A is selected from A1When the compound B is obtained as B1The specific synthetic route is as follows:
Figure BDA0002077821320000141
when the 4, 7-dibromo-benzimidazole compound A is selected from A2When the compound B is obtained as B2The specific synthetic route is as follows:
Figure BDA0002077821320000142
specifically, in step S12, obtaining a compound C, and performing a Stille coupling reaction on the compound B and the compound C under the catalytic condition of bis-triphenylphosphine palladium dichloride or tetrakis-triphenylphosphine palladium to obtain a compound D. As a preferred embodiment, the step of Stille coupling reaction comprises: and (3) obtaining the compound C, and carrying out reflux reaction on the compound B and the compound C for 8-48 hours under the conditions that a solvent is tetrahydrofuran, a catalyst is bis-triphenylphosphine palladium dichloride or tetrakis-triphenylphosphine palladium, and the temperature is 80-130 ℃, so as to obtain a compound D. More preferably, the molar ratio of said compound B to said compound C is 1: (2.2-3).
When the 4, 7-dibromo-benzimidazole compound A is selected from A1When the compound D obtained is D1The specific synthetic route is as follows:
Figure BDA0002077821320000143
when the 4, 7-dibromo-benzimidazole compound A is selected from A2When the compound D obtained is D2The specific synthetic route is as follows:
Figure BDA0002077821320000151
specifically, in the step S13, the compound D is subjected to a condensation ring-closure reaction under the catalysis of triethyl phosphite to obtain the compound E. As a preferred embodiment, the step of condensation ring closure reaction comprises: and carrying out reflux reaction on the compound D for 10-40 hours at the temperature of 160-200 ℃ under the conditions that the solvent is o-dichlorobenzene and the catalyst is the triethyl phosphite to obtain a compound E. More preferably, the molar ratio of said compound D to said triethyl phosphite is 1: (20-40).
When the 4, 7-dibromo-benzimidazole compound A is selected from A1When the compound E obtained is E1The specific synthetic route is as follows:
Figure BDA0002077821320000152
when the 4, 7-dibromo-benzimidazole compound A is selected from A2When the compound E obtained is E2The specific synthetic route is as follows:
Figure BDA0002077821320000153
specifically, in step S14, bromoalkane is obtained, and the nucleophilic substitution reaction is performed on the compound E and the bromoalkane under the conditions that the solvent is N, N-dimethylformamide and the neutralizing agent is potassium hydroxide, so as to obtain a compound F. As a preferred embodiment, the step of nucleophilic substitution reaction comprises: and (3) obtaining the brominated alkane, reacting the brominated alkane with the compound E for 8-24 hours at the temperature of 80-110 ℃ by taking the N, N-dimethylformamide as a solvent and the potassium hydroxide as a neutralizing agent to obtain a compound F. More preferably, the molar ratio of said compound E to said brominated alkane is 1: (3-8).
When the 4, 7-dibromo-benzimidazole compound A is selected from A1When the compound F is obtained as F1The specific synthetic route is as follows:
Figure BDA0002077821320000161
when the 4, 7-dibromo-benzimidazole compound A is selected from A2When the compound F is obtained as F2The specific synthetic route is as follows:
Figure BDA0002077821320000162
specifically, in the step S15, the compound F is subjected to a Vilsmeier-Haack reaction under phosphorus oxychloride conditions to obtain an aldehyde compound based on a benzimide. As a preferred embodiment, the step of Vilsmeier-Haack reaction comprises: and heating the compound F to react for 6-24 hours under the conditions that a solvent is N, N-dimethylformamide, a formylation reagent is the phosphorus oxychloride and the temperature is 80-90 ℃, so as to obtain the aldehyde compound based on the benzimide. More preferably, the molar ratio of said compound F to said phosphorus oxychloride is 1: (10-30).
When the 4, 7-dibromo-benzimidazole compound A is selected from A1The specific synthetic route of the aldehyde compound BH based on the benzimide is as follows:
Figure BDA0002077821320000163
when the 4, 7-dibromo-benzimidazole compound A is selected from A2The specific synthetic route of the aldehyde compound NH based on the benzimide is as follows:
Figure BDA0002077821320000171
the embodiment of the invention also provides an organic solar cell, which comprises a light-trapping active layer, wherein the light-trapping active layer contains the above-mentioned benzimidazole-based acceptor material or the benzimidazole-based acceptor molecule prepared by the above-mentioned method.
The organic solar cell provided by the embodiment of the invention has the advantages that since the active layer for light capture takes the above-mentioned receptor material based on the benzimide or the receptor molecule based on the benzimide prepared by the above-mentioned method as the active component, the active component has the absorption bandwidth of ultraviolet visible light spectrum (350-1200nm), has strong light absorption in an ultraviolet-visible light region (600- & ltSUB & gt- & gt 1000nm), narrow optical band gap, strong light absorption capacity, good sunlight capturing capacity, good solubility and other excellent performances, is applied to an active layer for light capturing of an organic solar cell device, has more matched energy level and higher carrier mobility with the existing wide-bandgap donor material, can be used for preparing organic solar cells with high current, high voltage and high energy conversion efficiency, and enables devices to have higher short-circuit current (12.75 mA/cm).2) The high open-circuit voltage (0.79V) and the high photoelectric conversion efficiency reach 5.85 percent, and the application prospect is wide.
As a preferred embodiment, the active layer is made of a phthalimide-based acceptor material and an electron donor for use in an organic solar cell device. The preparation method comprises the steps of mixing an acceptor material based on the benzimide and an electron donor material, adding a proper solvent chloroform or chlorobenzene, heating and stirring to completely dissolve the materials, spin-coating on conductive glass to prepare a layer of film, and preparing an electrode on the film to prepare a battery device.
As a preferred embodiment, the ratio of donor material to the phthalimide-based acceptor material or acceptor molecule in the light-trapping active layer is 1: (1-2), the light-trapping active layer further comprises 0-0.5% of an additive by taking the total mass of the light-trapping active layer as 100%. In the light trapping active layer material based on the benzimide, the ratio of a donor to an acceptor is 1: (1-2), namely the content of the acceptor material is between 50% and 66.7%, the content of the active layer component in the light capturing active layer can be 100%, namely the active layer only contains the acceptor material or the acceptor molecule and the donor material based on the benzimide; and a small amount of additives such as 1, 8-Diiodooctane (DIO) and the like can be added to improve the device interface and further improve the photoelectric conversion stability and efficiency of the device.
In some embodiments, the light harvesting active layer in the organic solar cell comprises 100% active material consisting of a donor and the acceptor compound of formula (i).
In some embodiments, the light harvesting active layer in the organic solar cell comprises 100% active material consisting of a donor and the acceptor compound of formula (ii).
In some embodiments, the light trapping active layer in the organic solar cell comprises 99.5% of an active component consisting of a donor and an acceptor compound of formula (i) and 0.5% of a 1, 8-diiodooctane additive.
In some embodiments, the light harvesting active layer in the organic solar cell comprises 99.5% of an active ingredient consisting of a donor and an acceptor compound of formula (ii) and 0.5% of a 1, 8-diiodooctane additive. .
In some embodiments, the light trapping active layer in the organic solar cell comprises an active component consisting of an acceptor compound of formula (i) and an acceptor compound of formula (ii) as donors and 1, 8-Diiodooctane (DIO). As a preferred embodiment, the electron donor material is at least one selected from the group consisting of PBDB-T, PTB7-th, J61, J71, PBDB-T-2F and PBDB-T-2Cl, having the following structural formula:
Figure BDA0002077821320000181
in order to clearly understand the details and operation of the above-described embodiments of the present invention for those skilled in the art, and to clearly show the advanced performance of the embodiments of the present invention based on the phthalimide-based receptor material, the preparation method and the application thereof, the above-described technical solutions are illustrated below by way of a plurality of examples.
Example 1
A method for preparing receptor molecule BH-CN based on benzimide is shown as the synthetic route in figure 1:
s10, using a compound A1
Figure BDA0002077821320000191
Synthesizing aldehyde compound BH based on benzimide as raw material.
① mixing Compound A1(4.3g, 10.3mmol) was dissolved in concentrated sulfuric acid/fuming nitric acid (30mL/75mL), the reaction was refluxed at 90 ℃ for 15 hours, then cooled to room temperature, and then gradually poured into ice water. Sodium hydroxide was added to the solution. The precipitate is then filtered off and then purified by means of a silica gel column (mobile phase: petroleum ether and dichloromethane) to give B as a white solid1(3.4g，65.1％)，MS(EI，m/z)506.9。
② mixing of Compound B1(3.4g, 6.7mmol) and trimethyl- (6-octylthienoselenophene) tin (11.1g, 24.0mmol) were dissolved in 100mL of anhydrous toluene. Ar (Ar)2Pd (PPh) under protection3)4(0.8g, 0.69mmol) was added to the reaction solution, and the mixture was stirred under reflux at 120 ℃ for 24 hours. Cooling the reaction solution to room temperature, extracting with ethyl acetate, purifying the crude product with silica gel column to obtain a mobile phase of petroleum ether and ethyl acetate, and purifying with column to obtain yellow solid compound D1(3.2g，3.4mmol，50.7％)，MS(EI，m/z)945.2。
③ reaction of Compound D1(3.2g, 3.4mmol) in Ar2Adding into o-dichlorobenzene (80mL) under protection, heating to 190 ℃, then adding triethyl phosphite (3.0g, 19mmol) dropwise into the reaction system, and refluxing and stirring for 12 hours. After cooling to room temperature, the product compound E is distilled under reduced pressure1(2.8g, 3.2mmol, 94.1%) was used directly in the next step.
④ reaction of Compound E1(2.8g, 3.2mmol), 1-bromo-2-hexyloctane (7.1g, 23.4mmol), potassium iodide (0.52g, 3mmol) and potassium hydroxide (1.3g, 23.4mmol) were dissolved in 120mL of N, N-dimethylformamide. Reacting at 100 deg.C for 12 hr under nitrogen protection, cooling the reaction solution to room temperature, extracting with ethyl acetate, mixing organic layers, spin drying, and purifying with silica gel columnPurifying with petroleum ether and ethyl acetate as eluent, and purifying with column to obtain light yellow solid compound F1(3.4g，2.5mmol，79.2％)。MS(ESI，m/z)[M+H]+1334.7。
⑤ mixing of Compound F1(3.4g, 2.5mmol) was dissolved in N, N-dimethylformamide (100 mL). The reaction solution was stirred at 0 ℃ for half an hour under nitrogen, after which 6mL of POCl was added3Slowly added to the system, reacted at 0 ℃ for 2 hours, followed by reflux at 90 ℃ for 12 hours, after which the reaction solution was extracted with dichloromethane and purified by a silica gel column to obtain a benzimide-based aldehyde compound BH (2.5g, 1.8mmol, 72.0%) as an orange yellow solid. MS (ESI, M/z) [ M + H ]]+1385.5。
S20. mixing the aldehyde compound BH (2.5g, 1.8mmol) based on the benzimide and 1, 1-dicyano methylene-3-indanone
Figure BDA0002077821320000201
(3.7g, 19mmol) was dissolved in 200mL of chloroform, 10mL of pyridine was added, the mixture was heated under reflux and stirred overnight under nitrogen, after which the reaction mixture was cooled to room temperature, a certain amount of distilled water was added, followed by extraction with chloroform, and the crude product was purified by a silica gel column to obtain receptor molecule BH-CN (1.8g, 1.04mmol, 57.8%) as a deep blue solid, MS (TOF, M/z) [ M + H ]]+1738.8。1HNMR(400MHz，CDCl3)δ8.13(s，2H)，7.34(dt，J＝7.6，3.6Hz，4H)，7.21(dt，J＝7.6，3.4Hz，4H)，3.74(d，J＝6.8Hz，2H)，3.65(d，J＝7.2Hz，4H)，1.34-1.28(m，3H)，1.25-1.04(m，32H)，0.92-0.75(m，18H)。
The absorption spectrograms of the receptor molecule BH-CN based on the benzimide prepared in the embodiment of the invention in chloroform solution and thin film are shown in figure 3. As can be seen from fig. 3, the receptor molecule BH-CN based on benzimide prepared in the embodiment of the present invention has a very wide absorption band (350nm-1200nm), a strong light absorption in the uv-visible light region (600-1000nm), a narrow optical band gap (1.18eV), a better matching energy level and a higher carrier mobility compared with the existing donor material with a wide band gap, and can improve the photoelectric conversion efficiency.
The cyclic voltammogram of the receptor molecule BH-CN based on the benzimide prepared in the embodiment of the invention is shown in the attached figure 4. As shown in the attached figure 4, the acceptor molecule BH-CN based on the benzimide prepared by the embodiment of the invention has a HOMO energy level of-5.51 eV and a LUMO energy level of-3.86 eV, and the energy gap is smaller, so that the electron transfer is facilitated.
Example 2
A method for preparing a receptor molecule NH-CN based on benzimide, which is shown as a synthetic route in the attached figure 2:
s10, using a compound A2
Figure BDA0002077821320000202
An aldehyde compound NH based on the benzimide is synthesized as a raw material.
① mixing Compound A2(4.1g, 6.3mmol) was dissolved in concentrated sulfuric acid/fuming nitric acid (30mL/75mL), the reaction was refluxed at 90 ℃ for 15 hours, then cooled to room temperature, and then gradually poured into ice water. Sodium hydroxide was added to the solution. The precipitate is then filtered off and then purified by means of a silica gel column (mobile phase: petroleum ether and dichloromethane) to give compound B as a white solid2(3.4g，4.6mmol，73.0％)，MS(EI，m/z)736.1。
② mixing of Compound B2(3.4g, 4.6mmol) and trimethyl- (6-octylthienothiophene) tin (10.5g, 22.7mmol) were dissolved in 100mL of anhydrous toluene. Ar (Ar)2Pd (PPh) under protection3)4(0.8g, 0.69mmol) was added to the reaction solution, and the mixture was stirred under reflux at 120 ℃ for 24 hours. Cooling the reaction solution to room temperature, extracting with ethyl acetate, purifying the crude product with silica gel column to obtain a mobile phase of petroleum ether and ethyl acetate, and purifying with column to obtain a brown yellow solid compound D2(2.7g，2.3mmol，50.3％)，MS(ESI，m/z)[M+H]+1177.3。
③ reaction of Compound D2(2.7g, 2.3mmol) in Ar2Adding into o-dichlorobenzene (70mL) under protection, heating to 190 ℃, then adding triethyl phosphite (3.0g, 19mmol) dropwise into the reaction system, and refluxing and stirring for 12 hours. Cooling to room temperature, and distilling under reduced pressure to obtain a product compound E2(2.5g), used directly in the next step.
④ reaction of Compound E2(2.5g, 2.2mmol), 1-bromo-2-hexyloctane (7.1g, 23.4mmol), potassium iodide (0.52g, 3mmol) and potassium hydroxide (1.3g, 23.4mmol) were dissolved in 120mL of N, N-dimethylformamide. Reacting at 100 deg.C for 12 hr under nitrogen protection, cooling the reaction solution to room temperature, extracting with ethyl acetate, mixing the organic layers, spin-drying, purifying with silica gel column, eluting with petroleum ether and ethyl acetate to obtain light yellow solid compound F2(2.1g，1.34mmol，60.9％)。MS(EI，m/z)[M+H]+1561.1。
⑤ mixing of Compound F2(1.8g, 1.15mmol) was dissolved in N, N-dimethylformamide (80 mL). The reaction solution was stirred at 0 ℃ for half an hour under nitrogen, after which 4mL of POCl was added3Slowly added to the system, reacted at 0 ℃ for 2 hours, followed by reflux at 90 ℃ for 12 hours, after which the reaction solution was extracted with dichloromethane and purified by a silica gel column to obtain an orange-yellow solid of the benzimide-based aldehyde compound NH (1.4g, 0.87mmol, 75.7%). MS (ESI, M/z) [ M + H ]]+1617.8。
S20. mixing aldehyde compound NH based on benzimide (0.8g, 0.49mmol) and 1, 1-dicyano methylene-3-indanone
Figure BDA0002077821320000211
(1.8g, 0.93mmol) was dissolved in 100mL of chloroform, 5mL of pyridine was added, the mixture was heated under reflux under nitrogen for overnight stirring, after which the reaction solution was cooled to room temperature, a certain amount of distilled water was added, followed by extraction with chloroform, and the crude product was purified by a silica gel column eluting with chloroform as a mobile phase to give a dark green solid, a benzimide-based acceptor molecule NH-CN (480mg, 0.24mmol, 49.0%), MS (TOF, M/z) [ M + H ]]+1969.9。1HNMR(400MHz，CDCl3)δ8.14(s，2H)，7.36(dt，J＝7.4，3.7Hz，4H)，7.21(dt，J＝7.2，3.2Hz，4H)，3.76(d，J＝6.8Hz，4H)，3.65(d，J＝7.2Hz，4H)，1.39-1.28(m，4H)，1.25-1.03(m，32H)，0.93-0.72(m，24H)。
The absorption spectrograms of the receptor molecule NH-CN based on the benzimide prepared in the embodiment of the invention in chloroform solution and thin film are shown in figure 5. As can be seen from fig. 5, the receptor molecule NH — CN based on benzimide prepared in the embodiment of the present invention has a very wide absorption band (350nm to 1200nm), a strong light absorption in the uv-visible light region (600-1000nm), a narrow optical band gap (1.07eV), a better matching energy level and a higher carrier mobility compared with the existing donor material with a wide band gap, and can improve the photoelectric conversion efficiency.
The cyclic voltammogram of the receptor molecule NH-CN based on the benzimide prepared by the embodiment of the invention is shown in the attached figure 6. As shown in the attached figure 6, the acceptor molecule BH-CN based on the benzimide prepared by the embodiment of the invention has a HOMO energy level of-5.54 eV and a LUMO energy level of-3.90 eV, and the energy gap is smaller, so that the electron transfer is facilitated.
Example 3
An organic solar cell device based on a receptor molecule BH-CN of benzimide.
Preparing a device: according to the receptor molecule BH-CN based on the benzimide prepared in the embodiment 1 of the invention, a commercial PTB7-th is used as a donor material, the donor material and the receptor material are weighed according to a ratio of 1:1.5, chloroform is used as a solvent, 1, 8-Diiodooctane (DIO) is used as an additive, the mixture is stirred uniformly and then spin-coated, and then the wafers are subjected to annealing treatment at different temperatures. And after the treatment is finished, the scraping cathode is used as an anode contact of the device. Then, the negative electrode was evaporated with aluminum.
Photovoltaic performance: according to the structure of the device: ITO/PEDOT PSS/PTB 7-th: BH-CN/PDINO/Al is used for manufacturing an organic solar cell, and the performance of the device is tested, and the test results are shown in the following table 1 and the attached figure 7.
TABLE 1
Figure BDA0002077821320000221
As can be seen from Table 1 and FIG. 7, the organic solar cell prepared by using the acceptor molecule BH-CN based on the benzimide and the commercialized PTB7-th as the donor material in the embodiment of the present invention has a high short-circuit current (12.75 mA/cm)2) And energyThe conversion efficiency (5.85%) and wide application prospect.
Example 4
An organic solar cell device based on a receptor molecule NH-CN of a benzimide.
Preparing a device: according to the receptor molecule NH-CN based on the benzimide prepared in the embodiment 2 of the invention, the commercialized PTB7-th is used as a donor material, the donor material and the receptor material are weighed according to the ratio of 1:1.5, chloroform is used as a solvent, 1, 8-Diiodooctane (DIO) is used as an additive, the mixture is stirred uniformly and then is subjected to spin coating, and then the wafers are subjected to annealing treatment at different temperatures. And after the treatment is finished, the scraping cathode is used as an anode contact of the device. Then, the negative electrode was evaporated with aluminum.
Photovoltaic performance: according to the structure of the device: ITO/PEDOT PSS/PTB 7-th: organic solar cells are manufactured by NH-CN/PDINO/Al, and performance tests are carried out on the devices, and the test results are shown in the following table 2 and the attached figure 8.
TABLE 2
Figure BDA0002077821320000222
Figure BDA0002077821320000231
As can be seen from the above Table 2 and the attached FIG. 8, the organic solar cell prepared by using the acceptor molecule NH-CN based on the benzimide and the commercialized PTB7-th as the donor material in the embodiment of the present invention has a high short-circuit current (9.45 mA/cm)2) And energy conversion efficiency (4.20%), and has wide application prospect.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (10)

1. A phthalimide-based receptor material, comprising at least one active ingredient of a compound of formula (i) and a compound of formula (ii):
Figure FDA0002077821310000011
wherein R is11、R12、R21、R22、R31、R32Are each independently selected from C6～C30An alkyl chain of (a); y is selected from sulfur or selenium; x1And X2Is an electron-withdrawing unit, said X1And X2Each independently selected from any one of the following electron withdrawing groups:
Figure FDA0002077821310000012
wherein R is4Selected from: any one of hydrogen, fluorine, chlorine, cyano, methoxy, sulfoxy and methyl, and T is selected from: any one of oxygen, sulfur and selenium.
2. The phthalimide-based acceptor material of claim 1, wherein C is6～C30The alkyl chain of (a) is: c8H17-＊、
Figure FDA0002077821310000013
Any one of them; and/or the presence of a gas in the gas,
said X1And X2Each independently selected from:
Figure FDA0002077821310000014
3. the phthalimide-based acceptor material of claim 1 or 2, wherein the R is11And R12Selected from the same said C6～C30Said R is21And R22Selected from the same said C6～C30Said R is31And R32Selected from the same said C6～C30An alkyl chain of (a);
said X1And X2Selected from the same said electron withdrawing groups.
4. A method for preparing a phthalimide-based receptor molecule, comprising the steps of:
obtaining an aldehyde compound and an electron-withdrawing compound based on the benzimide;
obtaining a weakly basic catalyst, dissolving the catalyst, the aldehyde compound based on the benzimide and the electron-withdrawing compound in an organic solvent, and refluxing for 12-24 hours at the temperature of 60-70 ℃ to obtain a receptor molecule based on the benzimide;
wherein the benzimide-based aldehyde compound is selected from the group consisting of:
compound BH
Figure FDA0002077821310000021
Or compound NH
Figure FDA0002077821310000022
The electron-withdrawing compound is selected from any one of the following compounds:
Figure FDA0002077821310000023
wherein R is1、R2、R3Are each independently selected from C6～C30Y is selected from sulfur or selenium, R4Selected from: any one of hydrogen, fluorine, chlorine, cyano, methoxy, sulfoxy and methyl, and T is selected from: any one of oxygen, sulfur and selenium.
5. The method of preparing a benzimide-based receptor molecule according to claim 4, wherein the molar ratio of the benzimide-based aldehyde compound to the electron-withdrawing compound is 1: (8-20); and/or the presence of a gas in the gas,
the weakly basic catalyst is selected from: piperidine, pyridine or quinoline; and/or the presence of a gas in the gas,
the organic solvent is selected from: chloroform or dichloromethane; and/or the presence of a gas in the gas,
said C is6～C30The alkyl chain of (a) is: c8H17-＊、
Figure FDA0002077821310000031
Figure FDA0002077821310000032
Any one of them.
6. The method of preparing a benzimide-based receptor molecule according to claim 5, wherein the step of preparing the benzimide-based aldehyde compound comprises:
obtaining a 4, 7-dibromo-benzimide compound A, and carrying out nitration reaction under the conditions of concentrated sulfuric acid and fuming nitric acid to obtain a compound B;
obtaining a compound C, and carrying out Stille coupling reaction on the compound B and the compound C under the catalysis condition of palladium bis (triphenylphosphine) dichloride or palladium tetra (triphenylphosphine) to obtain a compound D;
carrying out condensation ring-closing reaction on the compound D under the catalysis of triethyl phosphite to obtain a compound E;
obtaining bromoalkane, and carrying out nucleophilic substitution reaction on the compound E and the bromoalkane under the conditions that a solvent is N, N-dimethylformamide and a neutralizing agent is potassium hydroxide to obtain a compound F;
carrying out Vilsmeier-Haack reaction on the compound F under the condition of phosphorus oxychloride to obtain an aldehyde compound based on the benzimide;
wherein the 4, 7-dibromo-benzimidazole compound A is selected from the following compounds:
Figure FDA0002077821310000033
or
Figure FDA0002077821310000034
The compound C is
Figure FDA0002077821310000035
Wherein Y is selected from sulfur or selenium; the brominated alkanes are selected from: c6～C30The brominated alkanes of (a);
when the 4, 7-dibromo-benzimidazole compound A is selected from A1Then preparing an aldehyde compound BH based on the benzimide, wherein the compound B, the compound D, the compound E and the compound F are respectively B1，D1，E1And F1Each structural formula is:
Figure FDA0002077821310000036
Figure FDA0002077821310000041
when the 4, 7-dibromo-benzimidazole compound A is selected from A2Then preparing an aldehyde compound NH based on the benzimide, wherein the compound B, the compound D, the compound E and the compound F are respectively B2，D2，E2And F2Each structural formula is:
Figure FDA0002077821310000042
wherein R is1、R2、R3Are each independently selected from C6～C30Alkyl chain of (2).
7. The method of preparing a phthalimide-based receptor molecule of claim 6, wherein the step of nitrating comprises: according to the volume ratio of the concentrated sulfuric acid to the fuming nitric acid being 1: (1-3) mixing the concentrated sulfuric acid and the fuming nitric acid to obtain a nitration reagent; carrying out nitration reaction on the 4, 7-dibromo-phthalimide compound A in the nitration reagent for 8-24 hours at the temperature of 80-100 ℃ to obtain a compound B; and/or the presence of a gas in the gas,
the step of the Stille coupling reaction comprises: obtaining the compound C, and carrying out reflux reaction on the compound B and the compound C for 8-48 hours under the conditions that a solvent is tetrahydrofuran, a catalyst is bis-triphenylphosphine palladium dichloride or tetrakis-triphenylphosphine palladium, and the temperature is 80-130 ℃ to obtain a compound D; and/or the presence of a gas in the gas,
the condensation ring-closure reaction comprises the following steps: carrying out reflux reaction on the compound D for 10-40 hours at the temperature of 160-200 ℃ under the conditions that a solvent is o-dichlorobenzene and a catalyst is the triethyl phosphite to obtain a compound E; and/or the presence of a gas in the gas,
the step of nucleophilic substitution reaction comprises: obtaining the brominated alkane, and reacting the brominated alkane with the compound E at the temperature of 80-110 ℃ for 8-24 hours by using the N, N-dimethylformamide as a solvent and the potassium hydroxide as a neutralizing agent to obtain a compound F; and/or the presence of a gas in the gas,
the Vilsmeier-Haack reaction step comprises: and heating the compound F to react for 6-24 hours under the conditions that a solvent is N, N-dimethylformamide, a formylation reagent is the phosphorus oxychloride and the temperature is 80-90 ℃, so as to obtain the aldehyde compound based on the benzimide.
8. The method of preparing a phthalimide-based receptor molecule of claim 7, wherein the mass ratio of compound a to the nitrating agent is 1: (10-30); and/or the presence of a gas in the gas,
the molar ratio of the compound B to the compound C is 1: (2.2-3); and/or the presence of a gas in the gas,
the molar ratio of the compound D to the triethyl phosphite is 1: (20-40); and/or the presence of a gas in the gas,
the molar ratio of the compound E to the brominated alkane is 1: (3-8); and/or the presence of a gas in the gas,
the molar ratio of the compound F to the phosphorus oxychloride is 1: (10-30).
9. An organic solar cell comprising a light trapping active layer, wherein the light trapping active layer comprises a benzimide-based acceptor material according to any one of claims 1 to 3 or a benzimide-based acceptor molecule prepared according to the method of any one of claims 4 to 8.
10. The organic solar cell of claim 9, wherein the ratio of donor material to the phthalimide-based acceptor material or acceptor molecule in the light-trapping active layer is 1: (1-2), the light-trapping active layer further comprises 0-0.5% of an additive by taking the total mass of the light-trapping active layer as 100%.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116768918A (en) * 2023-06-21 2023-09-19 深圳普太科技有限公司 Benzoimide-based receptor material and preparation method and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104744676A (en) * 2015-03-30 2015-07-01 华南理工大学 Conjugated polymer containing 7H-pyrrolo [3,4-g] quinoxaline-6,8-diketone and application of conjugated polymer
CN106349252A (en) * 2015-07-15 2017-01-25 苏州大学 Compound based on indacenodithiophene and application of compound
CN107915661A (en) * 2016-10-05 2018-04-17 默克专利股份有限公司 Organic semiconductor compound
CN109328189A (en) * 2016-07-08 2019-02-12 默克专利股份有限公司 Condensed dithienothiophene derivative is used as organic semi-conductor purposes with it
CN109762003A (en) * 2019-02-26 2019-05-17 桂林理工大学 One kind is based on miscellaneous condensed ring conjugated molecular compounds of asymmetric selenium and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104744676A (en) * 2015-03-30 2015-07-01 华南理工大学 Conjugated polymer containing 7H-pyrrolo [3,4-g] quinoxaline-6,8-diketone and application of conjugated polymer
CN106349252A (en) * 2015-07-15 2017-01-25 苏州大学 Compound based on indacenodithiophene and application of compound
CN109328189A (en) * 2016-07-08 2019-02-12 默克专利股份有限公司 Condensed dithienothiophene derivative is used as organic semi-conductor purposes with it
CN107915661A (en) * 2016-10-05 2018-04-17 默克专利股份有限公司 Organic semiconductor compound
CN109762003A (en) * 2019-02-26 2019-05-17 桂林理工大学 One kind is based on miscellaneous condensed ring conjugated molecular compounds of asymmetric selenium and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116768918A (en) * 2023-06-21 2023-09-19 深圳普太科技有限公司 Benzoimide-based receptor material and preparation method and application thereof

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