基于类芴的格子纳米单体及其可溶性光电聚格设计

By means of the merits of fluorenes as the nanosynthons for the bottom-up fabrication of the complex macromolecular architectures, a family of nanopolymers should be created unprecedentedly via nanomonomer design. In this project, we will design the nanonomoners from fluorenes and fluorene-like molecular synthons or segments to examine the synthesis and polymerization methodology of polygrids. This project will start with the optimization of C(sp2)-C(sp3) coupling reactions of fluorene-like substrates, and then design optimized nanosynthons to afford nanogrids efficiently combining geometric configuration with supramolecular assistance derived from heteroatom-based fluorene-like structure. On that basis, diverse polymerization methods such as homopolymerization, copolymerization between different nanogrids and free radical polymerization will be developed to construct polygrids with various chain structure and extension models. In addition, a special route on polymerization first and then gridization of nanosynthons will be explored for the flexible methods. Finally, the multilevel structures will be characterized by combining organic NMR, Mass, polymeric GPC as well as nanotechnology such as TEM, SEM as well SEAD or GIXD and SANS. The platform of soluble organic nanopolymers under the project will offer state-of-the-art models to macromolecular physics, the relation between structures and optoelectronic parameters, polymer film processing, or the effective solution to plastic electronics.

凭借芴基共价纳米合成子在构建复杂拓扑结构过程中表现出的独特的优势,一系列前所未有的纳米聚合物结构正孕育而生。在该项目中，拟以芴与类芴为基本合成子设计纳米单体，开展纳米聚格的合成与聚合方法学研究。项目将从优化类芴的 C(sp2)-C(sp3) 偶联反应开始，将最佳几何构型匹配与芴、氮杂芴、环戊二噻吩以及吖啶等类芴基团超分子协助特性相结合设计最优化的纳米合成子，发展高效格子化反应制备纳米单元格；在此基础上，开展各类单元格的均聚、共聚以及自由基聚合等聚合方法，并探索先聚合后格子化制备聚格方法；最终，结合理论计算以及有机、高分子与纳米表征技术对纳米聚格进行相关研究。项目拟建立的可溶性纳米聚合物平台为高分子物理、高分子光电特性关系研究、高分子薄膜加工方法及其塑料电子器件应用提供新的模型与方案。

本项目围绕格芳烃和纳米聚格的设计、合成、光电性质研究及规律总结展开工作，在实施过程中，设计合成了一系列纳米尺度的格芳烃，通过探究格子化的合成条件、合成模式总结出了高效的格子化反应规律；探究出了实现高分子量的单元格聚合反应条件并发展了灵活高效的聚合模式，进而获得了以各类纳米格为单体的纳米手画手聚格、聚菱形格、共轭聚格。在以上基础上，论证了类芴基团在立体选择性格子化反应中的影响，制备出了高立体选择性的具有强抗塌陷能力的棒状骨架手画手聚格；实现了高介电常数、高迁移率的聚菱形格，具有可拉伸/弯曲的柔性力学特性、可实现角分辨蓝绿光发射转变的各向异性、超低波导损耗系数、高电致发光效率的光子晶体的介观组装等独特优势的共轭纳米聚格PODPFG，具有高度光稳定性和形貌稳定性的共轭纳米聚格PG-C8的制备。在格芳烃的理论计算、器件应用、功能修饰基团的光电性质研究、芴基光电性质的调控、立体异构等方面，也取得了一系列的研究成果。相关成果已经发表包括 Nature Communications, Research, Advanced Materials, Advanced Science, Chem, Advanced Functional Materials, Advanced Optical Materials 等 SCI期刊论文49篇，获授权专利23项和申请发明专利31项，培养已毕业博士3个，已毕业硕士17个，在读博士6个，在读硕士21个。