钯催化脱羧聚合制备新型聚合物半导体材料及其光电性能研究

Polymeric semiconductor photovoltaic materials, such as diketopyrrolopyrrole and isoindigo, have attracted much attention in the field of organic field effect transistors and organic solar cells for their high performance. Materials are the basis of organic optoelectronics research, and polymerization method is to obtain the material means. In view of the current preparation of DPP and isoindigo-based polymer, Stille or Suzuki polymerizations are widely used in which toxic or expensive catalysts are inavoidable. This project is based on a comprehensive literature and research experience of the applicant, drawing on recent progress in palladium-catalyzed coupling reactions decarboxylation, aimingto apply it to the polymerization reaction. The polymerization requires the polymerized units with higher activity, by screening different catalyst ligands and studied the influence of temperature, solvent, reaction time, etc., investigating the different reaction conditions according to different activity of polymerization units desired ultimately obtain catalyst system and the reaction conditions in preparing DPP and isoindigo-based polymers by decarboxylation polymerization. Prepared a series of new semiconductor polymer contained dithiazole unit based on this method, and study the bulk properties, obtain high-performance polymer organic semiconductor materials and devices.

聚合物半导体光电材料，如吡咯并吡咯二酮及异靛蓝等以其高性能在有机场效应晶体管及有机太阳能电池领域受到了广泛关注。材料是有机光电研究的基础，而聚合方法是获得材料的手段。鉴于当前制备吡咯并吡咯二酮及异靛蓝等各类聚合物广泛采用的Stille聚合或Suzuki聚合存在毒性大或者催化剂昂贵等弱点，本项目在综合文献报道和申请人工作经验的基础上，借鉴最近出现的钯催化脱羧偶联反应，将其应用于聚合反应。通过筛选不同的催化剂配体，并研究温度、溶剂、反应时间等的影响，考察不同活性聚合单元所需要的反应条件，最终得到脱羧聚合制备聚合物半导体材料所需要的催化体系及反应条件，为聚合物半导体材料的制备提供新的选择。并基于此方法制备系列新型聚合物半导体材料，研究其堆积及性能，得到高性能的聚合物有机半导体材料及器件。

聚合物半导体材料在有机场效应和有机发光器件领域受到广泛关注。本项目以二酮吡咯并吡咯单体和苯并噻二唑衍生物为骨架，通过在空间位阻的金刚烷基配体配位的钯催化剂的促进下进行的直接芳基化缩聚反应，设计合成了系列中聚物;进一步采用有机共晶的方式，设计合成了系利类超分子共晶材料。通过研究温度、溶剂、杂原子等因素的影响，从分子结构的设计来调控材料堆积方式，通过生长一维，二维单晶，单晶异质结，共晶等来研究分子间的作用力和生长机制；进一步通过构筑有机光电器件来研究材料分子的电荷传输机制；本项目相继开发了系列光电材料，包括有机场效应晶体管材料，有机光热材料，为相关领域的研究尤其是材料设计及组装调控提供了借鉴。项目实施以来，发表SCI论文9篇，项目组成员国内外报告10次，组织相关学术会议1次。