笼状有机微纳结构的组装、表征及其热力学和动力学机制研究

项目名称： 笼状有机微纳结构的组装、表征及其热力学和动力学机制研究

项目编号： No.21473154

项目类型： 面上项目

立项/批准年度： 2015

项目学科： 数理科学和化学

项目作者： 肖德宝

作者单位： 南京工业大学

项目金额： 95万元

中文摘要： 共价可控组装是当今国际化学和材料学的一项挑战。本项目将在前期工作基础上，探索以苝和卟啉衍生物为单元的有机纳米笼及其共价组装体的构筑，并对其光物理和催化性能进行系统研究，澄清其中的热力学和动力学。首先合成若干种苝和卟啉衍生物的多溴代物、联芳基二硼酸衍生物并用作结构单元，采用Suzuki交叉偶联方法构筑两种新型的共价组装体系：有机纳米笼及其一维共价组装体；然后探讨构筑单元和反应条件对产物及其复合体系的晶体结构和超分子结构的影响，澄清有机纳米笼以及有机纳米笼组装体形成中的若干热力学和动力学机制；澄清其中的光致电子过程、手性转移与放大、吸附和催化性能的调控机制；摸索产物光催化脱硫以及增效途径并澄清增效机制。通过对上述有机纳米笼及其一维共价组装体以及复合体系的结构与性能、组装体形成热力学和动力学机制的研究，从理论和物质两个层面为这类共价组装的有机多孔体系在新型功能材料体系中的应用奠定基础。

中文关键词： 有机微纳结构；分子自组装；笼状纳米结构；热力学；动力学

英文摘要： In our group,intensive researches on the construction of covalent organic frameworks and the manipulation of their structures and properties are being conducted. On this basis, we will in this project explore the construction of organic nanocages and their one-dimensional covalent assemblies,and investigate the structures, opto-physical properties and catalytic performance of the aformentioned materials and their composites using perylenes and porphyrins. Firstly, a series of tetrabromides and octabromides derived from perylene and porphyrin, and some biaromatic diboronic acids, will be synthesized, and be used as the building blocks to prepare the organic nanocages and their one-dimensional covalent assemblies using Suzuki crossing reaction under appropriate conditions. Secondly, thermodynamics and dynamics of material formation, the effects of building blocks and reaction conditions on crystal structures and supramolecular structures will be discussed. The manipulation mechanism of photo-induced electron process, chirality transfer and amplification, adsorption and catalytic performance will be further clarified.The ways and mechanism for improving the photocatalytic performances of nanocages and their covalent assemblies, and the catalytic oxidation performances of nanocages and their assemblies-supported metal nanoparticles for desulfuration and their corresponding infulencing factors will be fully clarified on an one-by-one basis. It is expected that the aforementioned investigations on the organic nanocages, their one-dimensional covalent assemblies and their nanocomposites, and their structures and properties, will technologically and fundamentally set the stage for the applications of those porous covalently assemblied organic materials in the fields such as next-generation optoelectronic materials, gas storage, molecule separation, catalysts and their supports.

英文关键词： organic micro/nano structure;molecular self-assembly;cage-shaped nanostructure;thermodynamics;dynamics