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CN-121991099-A - Benzothiazole non-condensed ring A-D-A' -D-A type-based organic solar cell receptor material and preparation method and application thereof

CN121991099ACN 121991099 ACN121991099 ACN 121991099ACN-121991099-A

Abstract

The application discloses a benzothiazole non-condensed ring A-D-A '-D-A type organic solar cell receptor material, a preparation method and application thereof, wherein a benzothiazole unit is taken as a central nuclear electron-withdrawing unit (A-unit), and then the benzothiazole unit, an electron-donating unit (D-unit) and a terminal group are synthesized into the organic solar cell receptor material with an A-D-A' -D-A structure. Wherein benzothiazole as an asymmetric central core structure can enhance the dipole moment of molecules, optimize intermolecular packing and improve the blending property of a donor and a receptor, and all the characteristics can jointly promote charge transmission to inhibit the double-molecule recombination. The molecular morphology is regulated and controlled by connecting different structural groups to the top branched chain, and meanwhile, different atoms can be introduced into the benzene ring to regulate and control the chemical energy level. In addition, the molecular aggregation and light absorption range can be regulated by accessing different end groups. The benzothiazole non-condensed ring A-D-A' -D-A type acceptor material provided by the application has the advantages of few synthesis and preparation steps, simple purification process and high yield.

Inventors

  • JIN YAOCHENG
  • Zheng Yamen
  • MO GUOYONG
  • CHEN HUOQUAN
  • LIU CHUYAN
  • HUO YANPING

Assignees

  • 广东工业大学

Dates

Publication Date
20260508
Application Date
20260130

Claims (10)

  1. 1. An organic solar cell receptor material based on benzothiazole non-condensed ring A-D-A' -D-A type is characterized in that the structure is shown as a general formula (I): ; (I); Wherein R 1 is independently selected from C 1 – C 100 alkyl and alkyl derivatives thereof, wherein one or more carbon atoms are replaced by oxygen atoms, alkenyl groups, alkynyl groups, aryl groups, hydroxyl groups, amino groups, carbonyl groups, carboxyl groups, ester groups, cyano groups and nitro groups, or one or more hydrogen atoms are replaced by fluorine atoms, oxygen atoms, alkenyl groups, alkynyl groups, aryl groups, hydroxyl groups, amino groups, carbonyl groups, carboxyl groups, ester groups, cyano groups or nitro groups, X 1 、X 2 is independently selected from hydrogen, fluorine, chlorine, bromine, cyano groups and nitro groups, D 1 、D 2 is an electron donating unit, and A 1 、A 2 is an electron withdrawing unit.
  2. 2. The benzothiazole non-condensed ring A-D-A' -D-A type organic solar cell receptor material according to claim 1, wherein D 1 、D 2 is selected from any one of the following structural formulas: ; Wherein X 3 is any one of hydrogen, fluorine, chlorine, bromine and iodine atoms independently, and the alkyl chain represented by R is a straight chain or branched chain with 1-100 carbon atoms, wherein 1 or more carbon atoms can be substituted by oxygen atoms, alkenyl groups, alkynyl groups, aryl groups, hydroxyl groups, amino groups, carbonyl groups, carboxyl groups, ester groups, cyano groups and nitro groups, and hydrogen atoms can be substituted by fluorine atoms, oxygen atoms, alkenyl groups, alkynyl groups, aryl groups, hydroxyl groups, amino groups, carbonyl groups, carboxyl groups, ester groups, cyano groups or nitro groups.
  3. 3. The benzothiazole non-condensed ring A-D-A' -D-A type organic solar cell receptor material according to claim 1, wherein A 1 、A 2 is selected from any one of the following structural formulas: ; Wherein X 4 is any one of sulfur, oxygen and selenium atoms independently, X 5 is any one of hydrogen, fluorine, chlorine, bromine and iodine atoms independently, and the alkyl chain represented by R is a straight chain or branched chain with 1-100 carbon atoms, wherein 1 or more carbon atoms can be substituted by oxygen atoms, alkenyl groups, alkynyl groups, aryl groups, hydroxyl groups, amino groups, carbonyl groups, carboxyl groups, ester groups, cyano groups and nitro groups, and the hydrogen atoms can be substituted by fluorine atoms, oxygen atoms, alkenyl groups, alkynyl groups, aryl groups, hydroxyl groups, amino groups, carbonyl groups, carboxyl groups, ester groups, cyano groups or nitro groups.
  4. 4. The preparation method of the benzothiazole non-condensed ring A-D-A' -D-A type organic solar cell receptor material is characterized by comprising the following steps: s1, synthesizing intermediates B1 and B2: Carrying out coupling reaction on trimethyl-stannane containing benzothiazole center core and D unit under the catalysis of tetra (triphenylphosphine) palladium to obtain 4, 7-bis [4, 4-bis (2-ethylhexyl) -4H-cyclopenta [2,1-B:3,4-B ' ] dithiophene-2-yl ] -2-heptyl benzo [ D ] thiazole B1, carrying out coupling reaction on 4, 7-dibromo-5, 6-difluoro-2-heptyl benzo [ D ] thiazole and [4, 4-bis (2-ethylhexyl) -4H-cyclopentadiene [2,1-B:3,4-B ' ] dithiophene-2-yl ] trimethyl-stannane under the catalysis of tetra (triphenylphosphine) palladium to obtain 4, 7-bis [4, 4-bis (2-ethylhexyl) -4H-cyclopenta [2,1-B:3,4-B ' ] dithiophene-2-yl ] -5, 6-difluoro-2-heptyl benzo [ D ] thiazole B2; s2, synthesizing monomers M1 and M2: introducing aldehyde group into B1 in S1 through Vilsmeier-Haack reaction to obtain 6,6'- (2-heptyl benzo [ d ] thiazole-4, 7-diyl) bis (4, 4-bis (2-ethylhexyl) -4H-cyclopenta [2,1-B:3,4-B' ] dithiophene-2-formaldehyde) M1, and introducing aldehyde group into B2 in S2 through Vilsmeier-Haack reaction to obtain 6,6'- (5, 6-difluoro-2-heptyl benzo [ d ] thiazole-4, 7-diyl) bis (4, 4-bis (2-ethylhexyl) -4H-cyclopenta [2,1-B:3,4-B' ] dithiophene-2-formaldehyde) M2; S3, synthesizing small molecule receptors Z1-Z2: Reacting M1 in S2 with chloroform as a solvent and 5, 6-difluoro-3- (dicyanomethylene) indidone under the catalysis of pyridine, performing Soxhlet extraction and recrystallization to obtain a final high-purity product Z1, reacting M1 in S2 with chloroform as a solvent and 5, 6-difluoro-3- (dicyanomethylene) indidone under the catalysis of pyridine, performing Soxhlet extraction and recrystallization to obtain a final high-purity product Z2, wherein the structural formulas of Z1 and Z2 are as follows: 。
  5. 5. The preparation method of the benzothiazole non-condensed ring A-D-A ' -D-A based organic solar cell acceptor material is characterized in that the molar ratio of 4, 7-dibromo-2-heptyl benzo [ D ] thiazole to [4, 4-bis (2-ethylhexyl) -4H-cyclopentadiene [2,1-b:3,4-b ' ] dithiophene-2-yl ] trimethyl-stannane in the catalysis of tetra (triphenylphosphine) palladium is 1 (2.0-2.1): 0.04-0.06), and the molar ratio of 4, 7-dibromo-5, 6-difluoro-2-heptyl benzo [ D ] thiazole to [4, 4-bis (2-ethylhexyl) -4H-cyclopentadiene [2,1-b:3,4-b ' ] dithiophene-2-yl ] trimethyl-stannane in the catalysis of tetra (triphenylphosphine) palladium is 1 (2.0-2.04-2.06).
  6. 6. The preparation method of the benzothiazole non-condensed ring A-D-A' -D-A type organic solar cell receptor material according to claim 5 is characterized in that the reaction is carried out under the protection of an organic solvent and nitrogen, the reaction temperature is 110-115 ℃, and the reaction time is 12-14 hours.
  7. 7. The preparation method of the benzothiazole non-condensed ring A-D-A' -D-A type organic solar cell acceptor material is characterized in that in S2, the molar ratio of B1 to Vilsmeier-Haack reagent (mixed solution of phosphorus oxychloride and N, N-dimethylformamide) is 1 (20-25), the molar ratio of B2 to Vilsmeier-Haack reagent (mixed solution of phosphorus oxychloride and N, N-dimethylformamide) is 1 (20-25), the reaction is carried out under the protection of organic solvent and nitrogen, the reaction is carried out in a dark place at room temperature, and the reaction time is 3-4 hours after adding the reagent at-1 ℃ and then heating to 95-100 ℃.
  8. 8. The method for preparing the benzothiazole non-condensed ring A-D-A' -D-A based organic solar cell acceptor material according to claim 4, wherein the molar ratio of M1 to 5, 6-difluoro-3- (dicyanomethylene) indigoid in S3 is 1 (4.5-5), the molar ratio of M2 to 5, 6-difluoro-3- (dicyanomethylene) indigoid is 1 (4.5-5), the reaction is carried out under the protection of 25-30 mL chloroform solvent and nitrogen under the protection of 0.3 mmol, the addition amount of pyridine is 0.5-0.7 mL, the reaction temperature is 65-70 ℃ and the reaction time is 9 h.
  9. 9. The method for preparing the benzothiazole non-condensed ring A-D-A' -D-A type organic solar cell receptor material according to claim 7, wherein the Soxhlet extraction is carried out after the completion of the reaction in S3, the solvent is cooled to room temperature and then is settled with methanol, and then the solvent is purified by a Soxhlet extractor with methanol, petroleum ether and methylene dichloride, so as to remove unreacted raw materials and residual catalyst. Then evaporating and concentrating the solution, and recrystallizing with methylene chloride serving as a good solvent and methanol serving as a poor solvent. The solid was collected by filtration and dried in vacuo to give four organic solar cell receptor materials based on benzothiazole non-fused ring types a-D-a' -D-a.
  10. 10. The use of the benzothiazole non-condensed ring a-D-a' -D-a based organic solar cell receptor material according to claims 1-3 for the preparation of organic solar cell devices.

Description

Benzothiazole non-condensed ring A-D-A' -D-A type-based organic solar cell receptor material and preparation method and application thereof Technical Field The application relates to the technical field of organic solar cells, in particular to a benzothiazole non-condensed ring A-D-A' -D-A-based organic solar cell receptor material, and a preparation method and application thereof. Background In recent years, the country has greatly advanced the construction of large photovoltaic bases. The importance of new energy sources reaches an unprecedented level. However, it has been difficult to increase the conversion rate as much as possible by using solar energy as the most stable energy source. Organic Solar Cells (OSCs) are a research hotspot for third-generation solar cells due to the advantages of light weight, flexibility, solution processing, suitability for large-scale preparation and the like. In recent years, the non-fullerene receptor (NFAs) gradually replaces the traditional fullerene receptor by virtue of the advantages of strong designability of molecular structure, wide light absorption range, flexible energy level regulation, adjustable crystallinity and the like, and promotes the photoelectric conversion efficiency of the organic solar cell to break through 21%. Among them, the A-D-A type (receptor-donor-receptor) condensed ring receptor is one of the most widely studied systems and most excellent in performance at present. The existing system receptor still has a plurality of technical bottlenecks, such as limited light absorption range, low photon capturing efficiency, limited open circuit voltage (V OC) of the device or aggravated carrier recombination, complex preparation process, and difficult mass production because part of receptor materials depend on expensive monomers or severe reaction conditions. Disclosure of Invention To overcome at least one of the problems of the prior art, it is a primary object of the present application to provide an organic solar cell receptor material based on benzothiazole non-condensed ring a-D-a' -D-a type. Through the atomic modification of the benzothiazole structural unit and the terminal end of the terminal group, the electronic structure of the material is regulated and controlled, and the reduction of the Highest Occupied Molecular Orbital (HOMO) energy level, the widening of the spectrum absorption range and the improvement of the matching property of the energy level and the typical donor material are realized. The four small molecule acceptor materials prepared have the advantages of simple synthetic route, adjustable optical band gap, proper energy level matching and the like, and are beneficial to improving the photoelectric conversion efficiency of the organic solar cell. The method provides a new design strategy for developing high-efficiency, stable and process-friendly acceptor materials. The second object of the present application is to provide a method for producing the above-mentioned benzothiazole non-condensed ring A-D-A' -D-A type organic solar cell receptor material. It is a third object of the present application to provide the use of the above-mentioned benzothiazole non-condensed ring type a-D-a' -D-a based organic solar cell receptor material. In order to achieve the above object, the present application provides the following solutions: the application provides a benzothiazole non-condensed ring A-D-A' -D-A type organic solar cell receptor material, which has a structure shown in a general formula (I): ; (I); Wherein R 1 is independently selected from C 1– C100 alkyl and alkyl derivatives thereof, wherein one or more carbon atoms are replaced by oxygen atoms, alkenyl groups, alkynyl groups, aryl groups, hydroxyl groups, amino groups, carbonyl groups, carboxyl groups, ester groups, cyano groups and nitro groups, or one or more hydrogen atoms are replaced by fluorine atoms, oxygen atoms, alkenyl groups, alkynyl groups, aryl groups, hydroxyl groups, amino groups, carbonyl groups, carboxyl groups, ester groups, cyano groups or nitro groups, X 1、X2 is independently selected from hydrogen, fluorine, chlorine, bromine, cyano groups and nitro groups, D 1、D2 is an electron donating unit, and A 1、A2 is an electron withdrawing unit. Preferably, D 1、D2 is selected from any one of the following structural formulas: ; Wherein X 3 is any one of hydrogen, fluorine, chlorine, bromine and iodine atoms independently, and the alkyl chain represented by R is a straight chain or branched chain with 1-100 carbon atoms, wherein 1 or more carbon atoms can be substituted by oxygen atoms, alkenyl groups, alkynyl groups, aryl groups, hydroxyl groups, amino groups, carbonyl groups, carboxyl groups, ester groups, cyano groups and nitro groups, and hydrogen atoms can be substituted by fluorine atoms, oxygen atoms, alkenyl groups, alkynyl groups, aryl groups, hydroxyl groups, amino groups, carbonyl groups, carboxyl groups, ester groups, cyano groups or nitro gr