{"title":"通过 C─H/C─H 氧化直接芳基化缩聚合成的苯甲醚可加工 n 型共轭聚合物,用于有机电化学晶体管。","authors":"Zerui Yu, Xingyu Jiang, Cheng Shi, Yibo Shi, Lizhen Huang, Yang Han, Yunfeng Deng, Yanhou Geng","doi":"10.1002/marc.202400757","DOIUrl":null,"url":null,"abstract":"<p><p>The development of n-type polymers for organic electrochemical transistors (OECTs) has lagged significantly behind their p-type counterparts. Moreover, these polymers are often synthesized via Stille polycondensation. Herein, three polymers with thiazole-flanked diketopyrrolopyrrole is synthesized as the monomer through C─H/C─H oxidative direct arylation polycondensation (Oxi-DArP). This protocol employs unfunctionalized (C─H terminated) monomers, and the generated byproducts are environmentally benign. The electron-deficient polymer backbone confers these polymers with LUMO energy levels below -4.20 eV, enabling all of them to exhibit n-type behavior in OECTs. Additionally, the resulting polymers are soluble in the green solvent anisole. With an optimized alkyl spacer between oligo(ethylene glycol) side chain and conjugated backbone, the polymer gTzDPP-C8 showed the best device performance with geometry normalized transconductance (g<sub>m,norm</sub>) up to 6.31 S cm<sup>-1</sup> and µC<sup>*</sup> up to 23.1 F V<sup>-1</sup> cm<sup>-1</sup> s<sup>-1</sup>. This work has successfully proved that C─H/C─H Oxi-DArP is a promising method for synthesizing n-type OMIECs to fulfill high-performance OECTs.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e2400757"},"PeriodicalIF":4.2000,"publicationDate":"2024-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Anisole Processible n-Type Conjugated Polymers Synthesized via C─H/C─H Oxidative Direct Arylation Polycondensation for Organic Electrochemical Transistors.\",\"authors\":\"Zerui Yu, Xingyu Jiang, Cheng Shi, Yibo Shi, Lizhen Huang, Yang Han, Yunfeng Deng, Yanhou Geng\",\"doi\":\"10.1002/marc.202400757\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>The development of n-type polymers for organic electrochemical transistors (OECTs) has lagged significantly behind their p-type counterparts. Moreover, these polymers are often synthesized via Stille polycondensation. Herein, three polymers with thiazole-flanked diketopyrrolopyrrole is synthesized as the monomer through C─H/C─H oxidative direct arylation polycondensation (Oxi-DArP). This protocol employs unfunctionalized (C─H terminated) monomers, and the generated byproducts are environmentally benign. The electron-deficient polymer backbone confers these polymers with LUMO energy levels below -4.20 eV, enabling all of them to exhibit n-type behavior in OECTs. Additionally, the resulting polymers are soluble in the green solvent anisole. With an optimized alkyl spacer between oligo(ethylene glycol) side chain and conjugated backbone, the polymer gTzDPP-C8 showed the best device performance with geometry normalized transconductance (g<sub>m,norm</sub>) up to 6.31 S cm<sup>-1</sup> and µC<sup>*</sup> up to 23.1 F V<sup>-1</sup> cm<sup>-1</sup> s<sup>-1</sup>. This work has successfully proved that C─H/C─H Oxi-DArP is a promising method for synthesizing n-type OMIECs to fulfill high-performance OECTs.</p>\",\"PeriodicalId\":205,\"journal\":{\"name\":\"Macromolecular Rapid Communications\",\"volume\":\" \",\"pages\":\"e2400757\"},\"PeriodicalIF\":4.2000,\"publicationDate\":\"2024-11-27\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Macromolecular Rapid Communications\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1002/marc.202400757\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"POLYMER SCIENCE\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Macromolecular Rapid Communications","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1002/marc.202400757","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
引用次数: 0
摘要
用于有机电化学晶体管(OECT)的 n 型聚合物的开发远远落后于 p 型聚合物。此外,这些聚合物通常是通过 Stille 缩聚法合成的。在此,我们通过 C─H/C─H 氧化直接芳基化缩聚(Oxi-DArP)合成了三种以噻唑侧翼二酮吡咯为单体的聚合物。该方案采用非官能化(C─H 端)单体,生成的副产品对环境无害。缺电子聚合物骨架使这些聚合物的 LUMO 能级低于 -4.20 eV,从而使它们在 OECTs 中均表现出 n 型特性。此外,这些聚合物还可溶于绿色溶剂苯甲醚。聚合物 gTzDPP-C8 在低聚(乙二醇)侧链和共轭骨架之间采用了优化的烷基间隔,显示出最佳的器件性能,几何归一化跨导(gm,norm)高达 6.31 S cm-1,µC* 高达 23.1 F V-1 cm-1 s-1。这项工作成功证明,C─H/C─H Oxi-DArP 是合成 n 型 OMIEC 以实现高性能 OECT 的一种可行方法。
Anisole Processible n-Type Conjugated Polymers Synthesized via C─H/C─H Oxidative Direct Arylation Polycondensation for Organic Electrochemical Transistors.
The development of n-type polymers for organic electrochemical transistors (OECTs) has lagged significantly behind their p-type counterparts. Moreover, these polymers are often synthesized via Stille polycondensation. Herein, three polymers with thiazole-flanked diketopyrrolopyrrole is synthesized as the monomer through C─H/C─H oxidative direct arylation polycondensation (Oxi-DArP). This protocol employs unfunctionalized (C─H terminated) monomers, and the generated byproducts are environmentally benign. The electron-deficient polymer backbone confers these polymers with LUMO energy levels below -4.20 eV, enabling all of them to exhibit n-type behavior in OECTs. Additionally, the resulting polymers are soluble in the green solvent anisole. With an optimized alkyl spacer between oligo(ethylene glycol) side chain and conjugated backbone, the polymer gTzDPP-C8 showed the best device performance with geometry normalized transconductance (gm,norm) up to 6.31 S cm-1 and µC* up to 23.1 F V-1 cm-1 s-1. This work has successfully proved that C─H/C─H Oxi-DArP is a promising method for synthesizing n-type OMIECs to fulfill high-performance OECTs.
期刊介绍:
Macromolecular Rapid Communications publishes original research in polymer science, ranging from chemistry and physics of polymers to polymers in materials science and life sciences.