2,6-薁和双噻吩酰亚胺共聚物的设计合成及载流子传输性能  

Design,synthesis and charge transport properties of conjugated copolymers based on 2,6-azulene and bi-thieno[3,4-c]pyrrole-4,6-dione

作　　者：汪洋 向焌钧 高希珂[1] Yang Wang;Junjun Xiang;Xike Gao(CAS Key Laboratory of Synthetic and Self-Assembly Chemistry for Organic Functional Molecules,Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences,Shanghai 200032,China)

机构地区：[1]中国科学院上海有机化学研究所,中国科学院有机功能分子合成与组装化学重点实验室,上海200032

出　　处：《科学通报》2024年第1期45-57,共13页Chinese Science Bulletin

基　　金：国家自然科学基金(22225506,22075310)资助。

摘　　要：本文通过聚合单体的理性设计和直接芳基化聚合策略,实现了薁基聚合物主链中薁单元偶极取向排列方式的精准调控,合成了3个基于2,6-薁和双噻吩酰亚胺的共轭聚合物P(AzBTPD-1)、P(AzBTPD-2)和P(AzBTPD-3),其主链中薁单元偶极排列方式分别为无规、偶极相反和偶极高度一致.通过紫外-可见吸收光谱和循环伏安法对聚合物的光谱和电化学性质进行研究.基于3个聚合物的有机场效应晶体管(OFET)器件均表现出n-型半导体特性,其中薁单元偶极取向排列高度一致的聚合物P(AzBTPD-3)表现出最优的器件性能,电子迁移率可达0.027 cm~2V^(-1)s^(-1).本工作精准调控了2,6-薁共轭聚合物主链中薁单元偶极取向的排列方式,为薁基聚合物的合成化学和结构-性能关系研究提供了新思路.Azulene,a nonalternant and nonbenzenoid hydrocarbon,has drawn increasing attention for constructing optoelectronic materials owing to its unique electronic structure and physicochemical properties.It is still a challenge to control the dipole orientation of azulene units in the backbone of 2,6-azulene-based conjugated polymers.Herein,three 2,6-azulene and bi-thieno[3,4-c]pyrrole-4,6-dione(BTPD)based conjugated copolymers P(AzBTPD-1),P(AzBTPD-2),and P(AzBTPD-3)with different dipole arrangements of azulene moieties were synthesized by direct arylation polymerization,where the rational design of the monomers allows for the achievement of the precisely controlled orientation of azulene units in the polymer main chain.The dipole arrangements of 2,6-azulene units were random for P(AzBTPD-1),head-to-head and tail-to-tail-arranged for P(AzBTPD-2)and head-to-tail-arranged for P(AzBTPD-3).High-temperature gel permeation chromatography of P(AzBTPD-1),P(AzBTPD-2),and P(AzBTPD-3)at 150°C with 1,2,4-trichlorobenzene as the eluent gave average molecular weight values of 20.8,20.7,and 24.1 k Da,respectively,with the corresponding polydispersity index values of 2.22,2.48,and 2.17,respectively.All three polymers have similar molecular weights,thereby the influence of molecular weight can be ignored.UV-vis absorption spectra and cyclic voltammetry were performed to evaluate the optoelectronic properties of these three polymers.The maximum absorption wavelength of P(AzBTPD-1),P(AzBTPD-2),and P(AzBTPD-3)in thin film showed red shifts(8,11 and 17 nm)relative to those in chloroform solution.The largest red shift of 17 nm of P(AzBTPD-3)indicated its strong intermolecular interactions in solid state.The energy levels of highest occupied molecular orbital(HOMO)and lowest unoccupied molecular orbital(LUMO)of P(AzBTPD-1),P(AzBTPD-2),and P(AzBTPD-3)were–5.27/–3.56 e V,–5.27/–3.58 e V and–5.27/–3.59 e V,respectively,which were acquired by cyclic voltammetry measurements.Due to the electron-withdrawing property of BTPD,these three

关 键 词：2 6-薁 双噻吩酰亚胺 共轭聚合物 偶极取向 有机场效应晶体管 

分 类 号：O633.5[理学—高分子化学]