基于氮杂稠环共轭聚合物材料的设计、合成与性能研究

Aza-fused pi-conjugated polymers have been exploited for diverse purposes due to their appealing structural and chemical properties. The preparation of such kind of functional materials with well-defined structures is in keen pursuit, in which the rational design and synthesis of building blocks play significant roles. 1,10-phenanthrolines represent an important class of Aza-fused molecules, and are utilized for many analytical and technological applications. However, until now, lacking of systematic and sophisticated synthetic strategies towards Aza-fused pi-conjugated macromolecules, especially the π-fused 1,10-phenanthroline derivatives has limited the development of this kind of polymeric materials and their applications in polymer-based chemosensors with high sensitivity and selectivity, optoelectronics etc. Therefore, the current proposal aims to exploit a simple and fruitful synthetic strategy to more elegant architectures of Aza-fused pi-conjugated macromolecules, and realize more advanced and complex functions from the fundamental molecular level. Specifically, we will design and synthesize 1,10-phenanthroline derivatives and analogues with fused polyaromatic groups at 3,4,7,8 ring positions as novel building blocks, and their corresponding conjugated polymers. Based on it, we could get more insights into the relationship between molecular structure and properties, and therefore, develop a new Aza-fused conjugated polymer sensing platform. Moreover, a comprehensive investigation of these phenanthroline based polymers will contribute to the application of such polymer systems in the fields of optoelectronics, biological probes and supramolecular materials. In summary, it is highly expected that the current proposal would further boost the preparation of Aza-fused pi-conjugated polymers for advanced and complex functional materials.

氮杂稠环共轭聚合物的制备和功能研究是高分子化学家与材料学家关注的热点和难点。作为一类重要的氮杂环，1,10-邻菲罗啉在分子探针、超分子自组装等方面具有重要价值。针对目前氮杂环体系，特别是具有大π结构的1,10-邻菲罗啉衍生物的合成方法有限、缺乏系统研究与优化等极大地限制了其聚合物种类及在高灵敏、高选择性聚合物荧光传感、检测与分子器件方面的应用这些问题，本项目期望通过合理的结构设计，建立高效的合成方法来发展3, 4, 7, 8位π扩展的可溶性稠环邻菲罗啉衍生物及类似物作为新型构筑基元，并制备相应的共轭聚合物。在此基础上实现新型氮杂稠环基聚合物荧光传感与检测平台的构建、表征及相关传感机制的考察，同时致力于拓展这类氮杂稠环聚合物在超分子自组装、光电功能材料等领域的应用。通过系统的研究，预期将为氮杂稠环基共轭聚合物材料的设计、多尺度结构控制和功能调控等方面提供新思路与新方法，促进该领域的发展。

氮杂稠环共轭聚合物的制备和功能研究是高分子化学家与材料学家关注的热点和难点。通过合理的结构设计，建立高效的合成方法来制备结构新颖、性能优异的氮杂稠环共轭聚合物，拓展新材料在荧光传感、光电功能材料等领域的应用一直是领域中的关键科学问题。本项目围绕氮杂稠环化合物及其共轭聚合物的设计、多尺度结构控制和功能调控等方面开展研究，主要结果包括以下三部分：.1. 基于稠环1,10-邻菲罗啉衍生物及类似物的共轭大分子的研究: 以Bischler-Napieralski关环反应为关键步骤，发展了π扩展的可溶性类稠环邻菲罗啉分子的合成新方法，合成了一系列新型的氮杂稠环共轭大分子，研究了其在细胞成像、液晶材料、荧光传感、力致荧光等方面的潜在应用。.2. 基于氮杂稠环共轭分子的共轭多孔聚合物的研究：制备并表征了一批结构新颖的基于氮杂稠环共轭分子的共轭多孔聚合物，利用其大的比表面积和稳定的微孔结构，拓展了这些聚合物在荧光传感、抗菌、染料吸附等方面的应用。.3. 基于氮杂稠环共轭分子的刺激响应性能的研究：设计合成了几类响应灵敏度高的基于哒嗪和硼氮单元的氮杂环共轭分子。系统研究了其构效关系和刺激响应行为，为探索氮杂稠环共轭材料的新功能和新用途奠定基础。.基于以上研究成果，项目承担人以通讯作者身份发表论文21篇，包括Angew. Chem. Int. Ed. 1 篇，J. Mater. Chem. C 2篇，Macromolecules 3篇等；做国际国内学术会议邀请报告7次；培养博士学位获得者2人，硕士学位获得者2人（1篇论文入选天津大学优秀博士论文）；入选天津市创新人才推进计划-中青年科技创新领军人才。