“预拆分金属配体/金属-有机配位基元”策略组装多中心集成手性分子笼

The key scientific topic of this project is to assemble multi-center integrated chiral metal-organic cages (MOCs) via pre-resoluted “metalloligand/metal-organic coordination unit” strategy. The research will start from the design, syntheses and pre-resolution of Fe/Co/Ni/Ru/Rh/Pd/Os/Ir/Pt metalloligands or metal-organic coordination units with different bonding strength and stereochemical stability, and serve them as face-directed, edge-directed, or vertex-directed chirality control elements, to assemble multi-center integrated chiral MOCs by further coordination with secondary metal nodes or linking ligands. By the incorporation, collaboration and spatial integration of pre-determined chirality units,other “active functional units”, and specific cavity effect in the converged chiral cage structure, potential applications in “effective recognition/separation of chiral guests and specific chiral-catalysis/photo-catalysis” can be achieved. The fundamental mechanism inherent in chiral MOCs’ assembling process and functional application will be explored, including bonding direction and regulation rule,chirality retention, transfer and amplification behavior, as well as synergistic “structure-performance” relationship among the multiple functional centers.

本项目的核心科学问题是基于金属配体和金属-有机配位基元的预拆分策略，构筑多中心集成的手性配位分子笼，并应用于手性客体分子识别/拆分和特异性手性催化/光催化。重点从具有不同键合强度和手性立体化学稳定性的Fe/Co/Ni/Ru/Rh/Pd/Os/Ir/Pt的金属配体/金属-有机配位基元的设计合成和预拆分出发，分别作为面导向、边导向或顶点导向的手性控制元素，进一步与第二金属节点或连接配体构筑组装多中心集成手性分子笼。通过预设手性基元和其他活性功能基元、以及分子笼特异空腔之间的空间匹配、性能协同和空间集成作用，实现高效的“手性客体分子识别/拆分、特异性手性催化/光催化”应用。揭示组装过程中的键合规律，手性保持、传递、放大等表现行为和多功能中心的协同构效作用机理。

本项目的研究目标和任务是基于金属配体和金属-有机配位基元的预拆分策略，构筑多中心集成的手性配位分子笼，研究其组装策略、主客体特性，并实现不同领域的功能应用。项目已按预定计划执行完成。发展了基于金属配体预拆分的分步组装策略构筑手性分子笼，探索了分子笼组装过程中的结构基础问题，基于金属立体构型手性中心的稳定化控制、手性分子动力学。研究了分子笼的主客体作用与光学响应特性，实现了光动力治疗与细胞成像结合的功能应用。在Angew. Chem. Int. Ed., Chem. Sci., Coord. Chem. Rev.等期刊上发表高水平研究论文20篇，获授权国家发明专利3件，申请国家发明专利1件。团队成员参加国内外学术会议并做邀请报告10余次。项目执行过程中，培养博士研究生3人，硕士研究生2人。