基于协同机制的金属基超分子聚合物的构筑与多组分自组装

Supramolecular polymer represents a novel class of macromolecules, in which self-assembly serves as a powerful tool and holds the monomeric units together via reversible noncovalent bonds. The precise control of the self-assembly process and the formation of highly-ordered functional supramolecular polymers are in keen pursuit, in which the rational choice of building blocks, as well as the deeper insight into supramolecular polymerization mechanism plays significantly important roles. For the conventional metallosupramolecular polymers, the steric hindrance exerted by metal-ligand complex commonly leads to the isodesmic polymerization mechanism, and hence results in the less-ordered assemblies. Therefore, the current proposal aims to pursue more ordered architectures and realize more complex functions from the fundamental molecular level. Specifically, we develop a novel metal-ligand building block with d8 electron configuration. The square planar propeties of Pt(??)-dpybH complex facilitate the combination of various noncovalent interactions, such as metal-ligand, metal-metal, π-π stacking and hydrogen interactions, which contribute to the formation of novel metallosupramolecular polymers with cooperative mechanism, and more importantly, exhibit superior propeties than the conventional metallosupramolecular polymers. Based on it, we could also get more insights into the synergistic effect of the multiple noncovalent interactions on the resulting supramolecular polymerization mechanism. Moreover, three potential supramolecular assemblies could be specifically achieved with the utilization of multicomponent self-assembly strategy in the controlled manner. A comprehensive understanding of the design principles, in combination with the detailed charge/energy transfer studies, will contribute to the the application of such supramolecular polymer systems in the field of optoelectronics. In summary, with the elaborate design of the buliding blocks and the precise manipulation of the self-assembly process, it is highly expected that the current proposal would benefit for further development of supramolecular materials.

通过自组装途径构建新型有序功能化超分子聚合物是高分子学科的重要发展方向。针对传统的金属基超分子聚合物中，络合物空间位阻相对较大，难以加合其他非共价键，导致聚合机制单一以及聚合物结构相对无序性等局限，本项目期望发展具有d8电子组态的低位阻金属络合物作为新型构筑基元，通过将多重非共价键驱动力进行有效加合，构建具有新型协同机制的金属基超分子聚合物，期望较传统的等构机制聚合物显示更为优越的特性，并力图掌握分子间弱相互作用的协同性对于超分子聚合机制以及聚合物性质的影响规律；通过多组分自组装的研究，实现特异性多组分聚集体的高选择性构建，并阐明单体单元的分子参数对于组装体可控性排列的影响规律，同时致力于拓展该类体系在电荷转移、能量传递光功能材料等领域的应用。通过系统深入的研究，预期将为金属基超分子组装体在驱动力及构筑基元的设计、组装体多尺度上的结构和功能调控等方面提供新思路，促进该领域的进一步发展。

通过自组装途径构建新型有序功能化超分子聚合物是高分子学科的重要发展方向。本项目针对传统的金属基超分子聚合物中，络合物空间位阻相对较大，难以加合其他非共价键，导致聚合机制单一以及聚合物结构相对无序性等局限，通过发展具有d8电子组态的低位阻金属络合物作为新型构筑基元，将多重非共价键驱动力进行有效加合，构建具有协同机制的金属基超分子聚合物，并掌握分子间弱相互作用的协同性对于超分子聚合机制的影响规律；通过对新型超分子聚合体系和聚合策略的研究，实现特异性多组分聚集体的高选择性构建，同时拓展了该类超分子软物质体系在光催化、光波导等功能材料领域的应用，为金属基超分子组装体在驱动力及构筑基元的设计、组装体多尺度上的结构和功能调控等方面提供了新的思路。在本基金的资助下，我们共发表SCI/EI论文23篇，其中，在影响因子>4.0的国际核心化学期刊上发表SCI论文19篇，包括Angew. Chem. Int. Ed. 1篇，Macromolecules 2篇，ACS Macro Lett. 1篇，Macromol. Rapid Commun. 2篇，Chem. Commun. 3篇，Org. Lett. 1篇及Polym. Chem. 6篇。所发表的论文被Chem. Rev.、Chem. Soc. Rev.等杂志进行大段篇幅并配图引用，入选爱思唯尔（Elsevier）“2014年中国高被引学者榜单（化学科学领域）”。鉴于我们工作的系统性和创新性，Lutz教授邀请我们在2015年斯特拉斯堡“第四届中法双边高分子与软物质研讨会”上做相关内容的汇报，江东林和薄志山教授邀请我们在2014年“中日功能超分子体系研讨会”上做相关内容的汇报。我们在2015年全国高分子学术论文报告会“高分子组装与超分子体系”分会做邀请报告。此外受邀在RSC旗下杂志Polymer Chemistry组织的主题为"2015 Emerging Investigators Themed Issue"的专刊上投稿。