手性硫醚功能化金属羧酸配位网络的设计合成及其性能研究

项目名称： 手性硫醚功能化金属羧酸配位网络的设计合成及其性能研究

项目编号： No.21201042

项目类型： 青年科学基金项目

立项/批准年度： 2013

项目学科： 无机化学

项目作者： 何军

作者单位： 广东工业大学

项目金额： 25万元

中文摘要： 手性研究对于生命科学的探索、药物开发以及材料科学发展都有着极其重要的意义。本研究将综合利用有机合成化学、晶体生长和固态化学等多个学科领域的研究方法，通过手性配体设计合成，实现手性配位网络的构筑和手性孔道的修饰。本项目拟利用手性硫醚芳香羧酸作为手性配体，根据软硬酸碱理论，硬酸金属离子会选择跟羧基形成三维开放式配位网络，而硫醚游离在孔道中。使用手性硫醚可以赋予目标配合物的纯手性，还可以通过手性硫醚的修饰来调控手性孔道的局部环境。重点考察不同手性环境的多孔配位网络对特定有机分子的吸附分离性能，探索结构的变化对其分离性能的影响，总结构效关系的规律，为开发新型手性分离材料提供更多的科学依据。从长远来看，手性硫醚功能化的金属-羧酸配位网络可以吸附具有催化活性的金属(Pd或Rh)。因此，该多孔材料还可用作担体负载金属并应用于异相选择性催化中。

中文关键词： 多孔配位网络；硫醚功能化；传感；吸附；催化

英文摘要： This proposal addresses the generic issues of assembly and systematic functionalization of homochiral metal-organic frameworks(MOFs), with the specific goal of achieving porous networks for high efficient enantioseparation. For this, we will take a crosscutting approach that integrates the knowledge of organic synthesis, crystal growth and coordination solid state chemistry. Our strategy here is to construct the frameworks from a class of rigid and symmetrical organic molecules containing two distinct sets of functional groups. One set is the chemically hard carboxylate groups at the terminal sites of the molecule as the primary group; the other is the thioether groups (-SR, with the soft S atom) at the central portion of the molecule as the seconday group. The crux is that chemically hard metal ions (such as Zn(II)) will selectively bond to the carboxylate groups to form a robust, porous MOF, while leaving the soft thioether groups free standing inside the established framework. By using a chiral thioether on the secondary group, we will be able to impose homochiral features on the framework. Moreover, we can also modify the secondary group to the provide accurate control over the local chiral environment of the pockets (e.g. hydrophobic or hydrophilic, the left- or right-handedness, binding sites for generatin

英文关键词： Porous coordination polymer；thioether functionalization；sensing；adsorption；catalysis