CN-117185960-B - Cyanated butadiene derivative, preparation method and application thereof, polymer semiconductor material, preparation method and application thereof

Abstract

The invention relates to the fields of organic synthesis and organic electronics, in particular to a cyanated butadiene derivative, a preparation method and application thereof, a polymer semiconductor material, a preparation method and application thereof, wherein the cyanated butadiene derivative has a structural general formula shown in the following formula (1) or formula (2): the invention develops a series of cyano butadiene derivative electron-deficient building units with simple structure, strong electron-withdrawing capability and simple synthesis. The electron-deficient structural unit can be used as an acceptor unit to be applied to development of organic photovoltaics, organic thermoelectricity and organic field effect transistor materials.

Inventors

• GUO XUGANG
• LI JIANFENG
• CHEN ZHICAI
• WANG JUNWEI
• LIU BIN

Assignees

• 南方科技大学
• 松山湖材料实验室

Dates

Publication Date

20260505

Application Date

20230728

Claims (8)

1. 1. A cyanated butadiene derivative, wherein the cyanated butadiene derivative is selected from any one of the following formulas TM1-TM 28: 。
2. 2. A process for the preparation of a cyanated butadiene derivative according to claim 1, comprising at least the steps of: And (3) reacting the benzene ring derivative containing the ortho diamine structure with lead tetraacetate to obtain the cyanated butadiene derivative.
3. 3. The method for producing a cyanated butadiene derivative according to claim 2, further comprising the step of reducing the benzene ring derivative containing an ortho-dinitro structure to obtain the benzene ring derivative containing an ortho-diamine structure.
4. 4. The process for producing a cyanated butadiene derivative according to claim 3, wherein the reduction of the benzene ring derivative containing an ortho dinitro structure is as follows: and reacting the benzene ring derivative containing the ortho-dinitro structure with zinc powder to obtain the benzene ring derivative with the ortho-diamine structure.
5. 5. A polymeric semiconductor material based on a cyanated butadiene derivative according to claim 1, wherein the polymeric semiconductor material is selected from any one of the following formulas P1-P11 and P25: Wherein n is an integer of 8-500.
6. 6. A method of preparing a polymeric semiconducting material according to claim 5, comprising at least the steps of: Synthesizing a polymer semiconductor material shown as a formula (3) by Stille coupling reaction of a formula (1) and a copolymer unit Ar2, wherein the formula (1) is a cyanated butadiene derivative as claimed in claim 1; the reaction formula is as follows: 。
7. 7. Use of a cyanated butadiene derivative as defined in claim 1 or a polymer semiconductor material as defined in claim 5 in an N-type polymer semiconductor.
8. 8. The use according to claim 7, wherein the N-type polymer semiconductor is used in any one of organic field effect transistors, organic thermoelectric devices, organic solar cells, organic light emitting diodes.

Description

Cyanated butadiene derivative, preparation method and application thereof, polymer semiconductor material, preparation method and application thereof Technical Field The invention relates to the fields of organic synthesis and organic electronics, in particular to a cyanated butadiene derivative, a preparation method and application thereof, a polymer semiconductor material, and a preparation method and application thereof. Background The polymer semiconductor material has the advantages of light weight, flexibility, solution processing and the like, and has unique advantages in the aspects of preparing large-area, full-flexibility and low-cost devices. Over several decades of effort by researchers, tremendous advances have been made in the performance of Organic Field Effect Transistors (OFETs). However, the development of the current N-type polymer semiconductor material (electron transport type) is relatively delayed compared with the P-type polymer semiconductor material (hole transport type), which restricts the commercial application of OFET. In the development of N-type polymer semiconductor materials, acceptor building blocks play a vital role. In the construction of the acceptor structural unit, the introduction of electron-deficient groups leads to reduced reactivity, which leads to increased synthesis difficulty and increased synthesis cost, so that the development of the acceptor structural unit with simple structure and simple synthesis is of great significance in promoting the development of N-type polymer semiconductor materials. Accordingly, the prior art is still in need of improvement and development. Disclosure of Invention The invention aims to solve the problems of complex structure, less types, difficult synthesis and the like of an electron-deficient unit in the development of an N-type polymer in the prior art, and provides a cyanated butadiene derivative, a preparation method and application thereof, a polymer semiconductor material, a preparation method and application thereof, and aims to overcome the defects. In order to achieve the aim of the invention, the invention is realized by the following technical scheme: In a first aspect, the present invention provides a cyanated butadiene derivative having a structural formula represented by the following formula (1) or formula (2): Wherein: In the formula (1), X, Y is respectively and independently selected from any one of H, F, cl, br, I, CN, NO 2、NR1R2, wherein R 1 and R 2 are respectively and independently selected from any one of H, C-C99 alkyl, alkenyl, alkynyl and amide groups, M, N is respectively and independently selected from any one of F, cl, br, I and sulfonate groups, and when X, Y is H, M, N is not bromine at the same time; In the formula (2), ar1 is selected from any one of substituted or unsubstituted thiophene, substituted or unsubstituted thiazole, substituted or unsubstituted thiadiazole, substituted or unsubstituted furan, substituted or unsubstituted selenophene, substituted or unsubstituted imide, substituted or unsubstituted benzene ring, substituted or unsubstituted pyridine, substituted or unsubstituted pyridazine and substituted or unsubstituted pyrazine, the substituent on Ar1 is selected from any one of C2-C99 straight chain, branched chain, ether chain, silane group chain, C3-C99 multi-ring-containing alkane chain and F, cl, br, I, CN, NO 2、NR3R4, wherein R 3 and R 4 are respectively and independently selected from any one of H, C-C99 alkyl, alkenyl, alkynyl and amide groups, and P, Q is respectively and independently selected from any one of F, cl, br, I and sulfonate groups. Preferably, the cyanated butadiene derivative is selected from any one of the following formulas TM1-TM 39; In a second aspect, the present invention also provides a process for the preparation of a cyanated butadiene derivative as described above, comprising at least the steps of: And (3) reacting the benzene ring derivative containing the ortho diamine structure with lead tetraacetate to obtain the cyanated butadiene derivative. Preferably, the benzene ring derivative containing the ortho-diamine structure is halogenated and then reacted with lead tetraacetate to obtain the cyanated butadiene derivative, and a typical reaction route can be referred to as the following steps: Step 1, adding the raw material 4 and liquid bromine into an acetic acid solution, and standing overnight at room temperature to obtain an intermediate 5; Step 2, adding the intermediate 5 and lead tetraacetate into toluene solution, and heating at 50-80 ℃ overnight to obtain the cyanated butadiene derivative TM2, wherein the reaction path is shown in the following formula: Preferably, the benzene ring derivative containing the ortho-diamine structure is halogenated and then reacted with lead tetraacetate to obtain the cyanated butadiene derivative, and a typical reaction route can be referred to as the following steps: step1, adding the raw material 7 and liq