具亲金属相互作用的手性超分子聚合物的构筑及其圆偏振发光行为研究

Supramolecular polymers represent a novel class of macromolecules, in which self-assembly serves as a powerful tool and holds the monomeric units together via reversible non-covalent bonds. Precise control over the self-assembly process and formation of highly-ordered functional supramolecular polymers are in keen pursuit. In our previous works, we have elaborately combined various non-covalent interactions, which contribute to the formation of novel supramolecular polymers with the nucleation-elongation cooperative mechanism. As compared to the traditional supramolecular polymers with the isodesmic mechanism, the cooperative supramolecular polymeric systems exhibit much superior properties. However, some problems still exist and need to be addressed, such as the limited building blocks, the lacking of extensive studies to realize their applications. To solve these issues, the current proposal aims to pursue various supramolecular polymers with the intriguing chiral and emission behaviors. Specifically, we sought to introduce non-covalent metallophilic interactions, which enable the emergence of phosphorescent signals at low energy visible light/NIR region. By taking advantage of the unique properties, we endeavor to exploit the potential applications of the resulting supramolecular polymers toward circularly polarised luminescent materials. Based on these studies, deeper insights into the effects of monomeric parameters on the functionality of the supramolecular polymers can be obtained. With the elaborate design of the building blocks and the precise manipulation of self-assembly process, the current proposal would benefit for the further development of novel functional materials on the basis of nucleation-elongation cooperative supramolecular polymeric systems.

构建结构有序且功能化的超分子聚合物是当前自组装领域的重要发展方向。申请人课题组在前期研究中，发展了具有仿生特性的“成核–链增长”协同机制超分子聚合物，相比于传统的等构机制超分子聚合体系，在聚合可控性和结构规整性等方面均展现出明显的优势。但针对其中构建基元和非共价驱动力的挖掘尚不充分、组装体功能拓展相对匮乏等问题，本申请项目拟将亲金属相互作用引入于“成核–链增长”协同超分子聚合物中，在低能量可见光/近红外光区域产生优异的磷光发光行为；并通过超分子手性信号的引入，进一步拓展该体系在圆偏振发光材料领域的功能应用。通过系统深入的研究，预期将为手性发光超分子聚合物在驱动力及构筑基元的设计、组装体的功能调控和功能拓展、以及阐明单体分子参数与组装体功能之间的关联性等方面提供新的思路，促进该领域的进一步发展。

构建结构有序且功能化的超分子聚合物是当前自组装领域的重要发展方向。本项目利用d8及d10电子组态的π–共轭有机金属分子作为构筑基元，通过非共价作用力的高效加合，构建结构规整的金属基超分子聚合体系，并通过各类亲金属相互作用力的引入，赋予该类组装体系独特的低能量可见光/近红外光区域磷光发光性能；进一步探索该类超分子聚合体系的圆偏振发光行为，拓展其在超分子光电材料领域的进一步应用。本项目已在国际核心化学期刊上发表通讯作者SCI论文27篇，包括J. Am. Chem. Soc. 1篇，Angew. Chem. Int. Ed. 4篇，Nat. Commun. 2篇，CCS Chem. 1篇,并受邀在Coord. Chem. Rev.杂志撰写综述。论文多次被Nat. Rev. Chem.、Chem. Soc. Rev.等杂志进行配图引用。2019年入选基金委优秀青年科学基金项目，2020年入选中国科学院青年创新促进会优秀会员，2020年获浙江省自然科学奖一等奖（排名第二），2021年获全国大环芳烃超分子化学学术新星奖。