刚性有机-无机杂化手性笼状化合物的设计、垂直交叉组装及表征

项目名称： 刚性有机-无机杂化手性笼状化合物的设计、垂直交叉组装及表征

项目编号： No.21202007

项目类型： 青年科学基金项目

立项/批准年度： 2013

项目学科： 有机化学

项目作者： 王金亮

作者单位： 北京理工大学

项目金额： 25万元

中文摘要： 近年来通过超分子自组装和动态共价化学搭建纳米尺度组装体的方法逐渐成为一类新颖的能源储存和转化材料，但如何将两者有机结合来深入挖掘其结构与功能之间的内在联系还处于摸索阶段。本项目利用金属-配体络合作用和亚胺缩合反应发展一系列不同拓扑结构（三棱柱和假六棱柱）的多金属中心的刚性具有多手性中心的金属化纳米笼的合成方法学。首次提出以手性配体(R)-联萘酚和联三吡啶和金属的络合物为构筑单元，研究多组分垂直交叉分步或一锅煮组装不同形状的笼状物，实现多组分多种作用力的可控自组装。研究超分子组装体功能单元结构与材料性能关系。通过测试其气体吸附性质，提高其对二氧化碳气体的选择性储存、分离、和转化性能。测试对带负电荷的客体分子的识别，尝试笼状物对不同客体分子的选择性包合和释放。通过笼内包裹染料敏化客体分子和轴手性的侧臂研究手性识别、分离和随后的光催化性能，建立高产率、高立体选择性、易分离的手性光催化体系。

中文关键词： 自组装；联三吡啶；笼状结构；亚胺缩合；弱相互作用

英文摘要： Recently, great effort has been devoted to the construction novel nano-size architecture for energy storage and transformation using supramolecular self-assembly by non-covalent interactions and dynamic covalent chemistry through reversible-covalent interactions. However, how to combine the advantage of these two strategies and further investigate the relationship between structure and properties is still in its infant stage. In this proposal, we will develop a series of shape-persistent, chiral, organic-inorganic hybrid nano-sized metallocage compounds with different topology structures and size through coordination-driven approach and imine condensation method. Here we present, for the first time, one step or "orthogonal" synthesis of prismatic cages consisting of 1,1′-bi-2-naphthol building blocks and terpyridine complexes in their backbone in high yield and highly accurate manner and the relationship between the chemical structures and properties. Investigation of the gas adsorption and selectivity of carbon dioxide of the metallocage will give the potential of application for carbon capture, storage system by molecular porous cage. Investigation of the recognition of host-guest molecules to realize the control of binding and release of guest molecules in different cages. Investigation of the effect of dy

英文关键词： self-assembly；teroyridine；cage structure；imine condensation reaction；intermolecular weak interaction