基于芳香酰胺寡聚物的配位笼状化合物组装及折叠性能

The use of coordination-driven self-assembly to build metal-organic cages with cavities is a frontier research topic in supramolecular chemistry, due to their important research value in molecular recognition, enzyme mimic, and molecular machines,. As biomimetic enzymes, the catalytic efficiency and selectivity of the metal-organic cages can not compare with those of the biological analogs, mainly because of the rigid structure. In this project, we will design and synthesize a series of foldable metal-organic cages based on aromatic amide oligomers. The project will focus on the investigation of the effect of amide groups on the folding performance, the relationship among the folding properties with cavity, and with chirality. The target of this project is to achieve the adjustable structure of the metal-organic cages, and ultimately to enhance their performance in molecular recognition, chirality induction and other aspects. The work would be of great importance to enrich and enhance the research on the structure and function of coordination-assembled compounds.

由于在分子识别、酶催化模拟、分子机器等方面的重要研究价值，利用配位组装方式构筑含有特定空腔的笼状化合物是超分子化学研究的一个前沿课题。受限于刚性配体结构，笼状化合物在仿生催化的效率和选择性上都与生物酶的性能相差较大。本申请项目拟以芳香酰胺寡聚物为配体，构筑一系列可折叠的配位笼状化合物。通过研究酰胺基团对折叠性能的影响规律，探索化合物的折叠性能与笼内空腔和手性的相互关系，最终实现笼状化合物的结构可调功能，提高其在分子识别，手性诱导等方面的性能。本项目工作将对丰富和提升配位组装化合物的结构和功能研究具有重要意义。

本项目以芳香酰胺寡聚物为配体，构筑了一系列具有折叠扭曲结构的配位笼状化合物，实现了其组装结构、手性性能的调控。取得的主要成果如下：一是利用芳香酰胺寡聚物配体构筑了M4L8型互锁的套笼化合物。研究表明，配体的扭曲性能够促进其分子间的芳香堆积和氢键作用，有利于组装体系的稳定。该研究为进一步发展新颖的人工分子机器奠定了良好的基础。二是在笼状化合物组装基础上，通过配位、浓度、客体诱导等手段实现了配体的逐步聚集及其组装体手性的逐级调控。这种逐级调控策略能够将手性信息分解为多个层级，并依次实现相应层级的控制。该研究为设计高性能分子开关和机器提供了支撑，为探索生命的手性起源提供了新的思路。