Semiconducting Polymers Based on Simple Electron‐Deficient Cyanated trans‐1,3‐Butadienes for Organic Field‐Effect Transistors

Abstract

AbstractDeveloping high‐performance but low‐cost n‐type polymers remains a significant challenge in the commercialization of organic field‐effect transistors (OFETs). To achieve this objective, it is essential to design the key electron‐deficient units with simple structures and facile preparation processes, which can facilitate the production of low‐cost n‐type polymers. Herein, by sequentially introducing fluorine and cyano functionalities onto trans‐1,3‐butadiene, we developed a series of structurally simple but highly electron‐deficient building blocks, namely 1,4‐dicyano‐butadiene (CNDE), 3‐fluoro‐1,4‐dicyano‐butadiene (CNFDE), and 2,3‐difluoro‐1,4‐dicyano‐butadiene (CNDFDE), featuring a highly coplanar backbone and deep‐positioned lowest unoccupied molecular orbital (LUMO) energy levels (−3.03–4.33 eV), which render them highly attractive for developing n‐type semiconducting polymers. Notably, all these electron‐deficient units can be easily accessed by a two‐step high‐yield synthetic procedure from low‐cost raw materials, thus rendering them highly promising candidates for commercial applications. Upon polymerization with diketopyrrolopyrrole (DPP), three copolymers were developed that demonstrated unipolar n‐type transport characteristics in OFETs with the highest electron mobility of >1 cm2 V−1 s−1. Hence, CNDE, CNFDE, and CNDFDE represent a class of novel, simple, and efficient electron‐deficient units for constructing low‐cost n‐type polymers, thereby providing valuable insight for OFET applications.