结构与功能导向的配位空腔的可控构筑及定向应用

Coordination cavity has been a hot area of inorganic chemistry in recent year because of its beautiful structure and wide application for selective recognition, adsorption and catalysis. Although some progresses have been achieved in recent years, there are also many problems; for example, synthesis of highly complex cavity is difficulty, function of cavity is limited. This project intends to construct novel coordination cavities based on reasonable ligand and strategy, and then realize their specific applications. This research consists of following two parts: Part I. Using flexible tridentate ligands and suitable metal ions to synthesize single coordination cavities with different sizes and chemical properties; and then controllable and reversible transformation of new-formed coordination cavities driven by appropriate external stimuli; finally, using such cavities to realize selective identification and catalysis of specific molecules. It is expect that we can develop a highly novel single coordination cavity that can be comparable to self-assembled aggregates from organism. Part II. Using specific ligands and suitable metal ions to prepare multi - coordination cavities, either display highly complex structure, or bear with specific functional group for corresponding applications; and then using such functional multi-coordination cavities to effectively remove the carbon dioxide from the exhaust gas from thermal power plant and the heavy metal ions from waste water. It is expected that we can finally develop several novel materials which have potential applications in industry.

配位空腔由于其结构优美，在选择性识别、吸附、催化等领域具有广泛的用途，是近年来无机化学学科的热点。尽管近几年该领域取得了一些进展，但还存在如合成高度复杂的空腔困难、空腔的功能有限等问题。本项目拟通过合理设计的配体与策略来可控构筑结构新颖的配位空腔，并实现其定向应用。研究内容包括两部分：一、利用灵活的三齿配体和合适的金属合成不同尺寸和化学性质的单配位空腔，并通过合适的外界刺激实现其可控转变，最终利用单配位空腔的特定尺度和化学性质来实现对特定分子的选择性识别、催化。期望最终能发展可以媲美生物体的，结构和功能都可调的单配位空腔。二、利用特定的配体和合适的金属来分别构筑高度复杂的多配位空腔，和带有特定功能基元的多配位空腔，并利用包含功能基元的多配位空腔高效去除热电厂尾气中的二氧化碳和污水中的重金属。并期望最终能发展具有潜在的工业应用前景的新材料。

如何实现配位空腔的可控构筑及定向应用是一个巨大的挑战，在该项目的资助下，我们合成了一系列结构新颖的含配位空腔的化合物，包括含配位笼，配位管，和多孔配位聚合物，并在外界刺激的诱导下实现了它们的可控、高效转变，最后利用合成的配位空腔还实现了对某些重要小分子的高效捕获，对某些重要化学反应的高效催化。