基于苯并二吲哚二酮的低聚物共轭长度调节及应用:共轭聚合物构建及载流子传输性能调控  

Conjugation Length Adjustment and Application of Oligomers Based on Benzodiindodione:Conjugated Polymer Construction and Carrier Transport Performance Regulation

作　　者：蔡厚继 谭若兮 董方亮 张杰[1] 胡正伟 赵海洋 刘春晨 王明 黄飞[1] 曹镛[1] Hou-ji Cai;Ruo-xi Tan;Fang-liang Dong;Jie Zhang;Zheng-wei Hu;Hai-yang Zhao;Chun-chen Liu;Ming Wang;Fei Huang;Yong Cao(State Key Laboratory of Luminescent Materials and Devices,School of Materials Science and Engineering,South China University of Technology,Guangzhou 510610;School of Materials Science and Engineering,Center for Advanced Low-dimension Materials,Donghua University,Shanghai 201620)

机构地区：[1]华南理工大学材料科学与工程学院、发光材料与器件国家重点实验室,广州510610 [2]东华大学材料科学与工程学院先进低维材料中心,上海201620

出　　处：《高分子学报》2025年第2期286-298,共13页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号U21A6002,52203355);广东省自然科学基金(基金号2023A1515012293);广州市科技计划项目(项目号2023A04J0970)资助.

摘　　要：有机共轭聚合物的载流子传输性能与共轭结构息息相关.然而,在分子水平上理解分子共轭长度与材料及器件性能的关系仍缺乏相关依据,设计和开发新型且共轭长度连续可控的结构单元在合成上面临挑战.基于此,本研究提供了一种新的分子设计和合成思路,通过氧化偶联的方式合成了一系列分子共轭长度可控的苯并二吲哚二酮衍生物的共轭低聚物,并将其构建成相应的聚合物,展示了其可调控的电子传输性能.随着中间构筑单元共轭长度的增加,材料的最低未占分子轨道(LUMO)能级逐渐降低,带隙变窄,传输性质由p型传输转变为双极型传输.含有单个苯并二吲哚二酮构筑单元的聚合物PBIDI-4F-T表现出了9.05×10^(-2) cm^(2)·V^(-1)·s^(-1)的最大电子迁移率和4.21×10^(-3) cm^(2)·V^(-1)·s^(-1)的最大空穴迁移率.本工作为探索电子受体低聚物单元共轭长度与聚合物载流子电荷传输性能之间的构效关系提供了新的参考.The carrier transport performance of organic conjugated polymers is closely related to the conjugated structure.However,there is still a lack of relevant principle for understanding the relationship between molecular conjugate length and the properties of materials and devices at the molecular level,and the design and development of units with continuous and controllable conjugate length faces challenges in synthesis.Based on this,this paper provides a new molecular design strategy and synthesis method,and synthesized a series of oligomers and corresponding polymers with controllable molecular conjugate lengths of benzodiindodione derivatives by oxidative coupling,and demonstrates their tunable charge transport performance.With the increase of the conjugate length of the intermediate building block,the lowest unoccupied molecular orbital(LUMO)energy level of the materials decreases gradually,the band gap narrows,and the charger carrier transport property changes from p-type to ambipolar transport characteristics.The polymer PBIDI-4F-T containing a single benzodiindodione building block exhibits the highest electron mobility of 9.05×10^(-2) cm^(2)·V^(-1)·s^(-1) and a hole mobility of 4.21×10^(-3) cm^(2)·V^(-1)·s^(-1).This work provides a new reference for exploring the structure-property relationship between the conjugate length of the acceptor oligomer units and the charge carrier transport performance of polymers.

关 键 词：低聚物 共轭聚合物 有机场效应晶体管 氧化偶联 一锅法 共轭延展 

分 类 号：O62[理学—有机化学]