圆柱状有机超分子胶囊的侧壁功能化及其应用研究

超分子胶囊具有类似于酶的空腔结构，能够加速或催化有机反应、稳定反应中间体，被广泛应用于物理有机化学研究。目前的胶囊结构通常高度对称，空腔缺少功能基团，大大地限制了其应用范围。因此，胶囊的侧壁修饰与空腔功能化是扩展其应用的必由之路。然而这又将导致合成路线的加长和组装异构体数目的增加，成为该研究领域的难点。本项目拟以脲基圆柱状超分子胶囊为基础，对其侧壁和空腔进行修饰。我们拟利用该胶囊的稳定特性，总结修饰超分子胶囊侧壁和空腔的通用策略。采用模版效应、空间位阻和自分类等策略，来控制超分子胶囊的异构化。在此可修饰超分子胶囊的基础上，通过侧壁将功能基团引入到胶囊空腔内，实现对胶囊空腔的按需剪裁，制备分子器件和分子反应容器。我们拟进一步利用超分子胶囊的隔离效应和稳定作用，使用NMR等常规分析手段监测部分有机化学反应中间体，揭示相应的反应机理。我们相信本项目的研究将为扩展超分子胶囊的应用奠定坚实的基础。

Supramolecular capsule, which possesses an isolated cavity analogous to enzyme's binding pocket, can accelerate or even catalyze some organic reactions and stabilize reactive intermediates. It has been widely applied to the study of physical organic chemistry. However, most of capsular structures known to date are highly symmetric and short of functional groups in their inner cavity, which greatly limit their application scope. Thus, modification of the walls and functionalization of the cavity of supramolecular capsules may be the only way to expand their applications. Nevertheless, this will inevitably results in longer synthetic route and greater number of possible assembly isomers, remaining one of obstacles in the development of this field. In this project, we would like to modify the walls and cavity of a cylindrical hydrogen-bonded supramolecular capsule based on urea binding motif. The high thermal stability of this capsule will make it a good platform for us to explore the general strategy on modifying supramolecular capsule's walls and cavity. Various strategies, such as template effect, steric repulsion and self-sorting, will be harnessed to control the isomerism of supramolecular capsule. On the basis of the resulting modifiable capsule, we will further tailor the capsule's cavity according to need through introducing functional groups on the walls, to construct molecular devices and molecular flasks. According to the isolation and stabilization properties of the functionalized supramolecular capsule, we may be able to monitor the reactive intermediates of some organic reactions with the routine analytic tools, such as NMR, and unravel the underlying reaction mechamism.We believe the research results of this project will lay a solid foundation for expanding the application of supramolecular capsules.