基于“镊合导向自组装”策略构筑新型超分子光功能材料

Supramolecular nanostructures represents a class of well-ordered architectures, in which self-assembly serves as a powerful tool and holds the building blocks together via reversible non-covalent bonds. The development of new self-assembly strategy is in keen pursuit, which is of paramount importance for the current supramolecular chemistry fields. Within this context, our research group has recently developed the “tweezering directed self-assembly” strategy, which demonstrates it high efficiency for the construction of precisely-defined supramolecular donor–acceptor assemblies. However, some problems still need to be addressed for such a novel self-assembly strategy, such as the limited non-covalent interactions employed, lack of extensive studies to realize the applications for the resulting assemblies, as well as the undefined structure-functionality relationships. To solve these issues, the current proposal aims to pursue various types of supramolecular architectures with intriguing photo-physical and photo-chemical behaviors, and furthermore take advantage of such optical properties for the achievement of supramolecular functional materials. Specifically, we sought to develop novel types of molecular tweezer/guest recognition motifs, which combine non-covalent metal-metal interactions with donor-acceptor interactions. Such highly directional non-covalent recognition motifs would be advantageous for the formation of higher-order supramolecular nanostructures and various soft matters, such as supramolecular gels and micelles. Furthermore, we endeavor to exploit the potential applications of the resulting supramolecular assemblies in the fields of visible-light-mediated organic synthesis and visible-light-triggered drug release. Based on these studies, we can get deeper insights into the effects of monomer and external parameters on the optical functionality of the resulting supramolecular nanostructures. With the elaborate design of the building blocks and the precise manipulation of self-assembly process, it is highly anticipated that the current proposal would benefit for the further development of novel supramolecular optically functional materials via the “tweeering-directed self-assembly" strategy.

发展新型超分子自组装方法构筑有序组装体并实现其功能化，是目前超分子化学领域的重要发展方向。申请人研究组近期发展了“镊合导向自组装”策略，在超分子共轭组装体的结构控制方面展示了优越的特性。但针对目前所发展的“镊合导向自组装”体系中，构建基元和驱动力的拓展不够深入、自组装调控行为相对缺乏、构建基元的光物理及光化学性质利用不充分、超分子组装体的功能应用开展较少等局限性，本申请项目拟将供受体作用与铂铂金属金属相互作用进行高效加合，构建新型超分子镊合组装体系，并实现其光学行为的高效调控，力图掌握分子及外界参数的改变对于超分子组装体光学行为的影响规律；进一步探索超分子组装体在光化学反应催化材料、光触发药物可控释放等领域的应用价值。通过系统深入的研究，预期将为“镊合导向自组装”策略在驱动力及构筑基元的设计、组装体多级多层次上的结构调控、超分子光功能材料的的构建等方面提供新思路，促进该领域的进一步发展。

利用非传统的非共价驱动力和组装策略实现有序超分子组装体的构筑与功能化，是当前超分子化学研究领域的重要研究方向。本项目在课题组前期建立的“镊合导向自组装”策略之基础上，通过铂-铂金属金属作用力的引入，构建了具有新颖光学行为的金属基超分子镊合体系，并探索该类体系在光功能材料领域的功能应用。项目执行期间主要针对含金属-金属键的超分子构建基元的探索、金属基超分子体系的刺激响应性、以及金属基超分子体系在光热、光催化材料等领域的功能化等方面展开了相应的研究，为新型驱动力及构筑基元的设计、组装体多级多层次上的结构调控、超分子材料的功能应用等方面提供新思路。在本项目的资助下，申请人已在国际核心化学期刊上发表SCI通讯作者论文28篇，包括Angew. Chem. Int. Ed. 3篇，Nat. Commun. 2篇，CCS Chem. 1篇，ACS Catalysis 1篇等。鉴于我们工作的系统性和创新性，受邀在Acc. Chem. Res.(2018)、Coord. Chem. Rev. (2020)等杂志上对研究工作进行综述和总结。参加国内外学术会议并做邀请/口头报告40余次，组织了第六届超分子化学青年学者论坛，并邀请了印度Subi J George教授、荷兰Sander Wezenberg教授、日本Daigo Miyajima教授等国内外专家学者进行学术访问和交流。汪峰获得2019年基金委优秀青年科学基金资助，并获得中科院青促会优秀会员（2019）。