基于多核金属簇单元构筑的无机-有机多孔杂化化合物的组装及性能研究

Inorganic-organic hybrid compounds are the new materials which have the advantages of inorganic and organic. The currently progressive impetus for the design and fabrication of novel inorganic-organic hybrid compounds is rooted not only in their fascinating structures but also from their promising properties in the field of gas storage, magnetism, and optical properties, and so on. Employment of related principle molecular designing and crystal engineering was used to modify and assemble the inorganic-organic hybrid materials and would be boost the novel topological frames and special functions of the sets, which has been greatly attracted in the materials field. However, the studies about polynuclear core of porous inorganic-organic hybrid compounds are relatively underdeveloped. That’s because it is difficult to control the metal clusters and design and synthesis of the porosity structure. In the research, the anion template would be introduced in synthesis system to increase the number of nuclear in metal clusters. From the synthetic point of view, secondary building units (SBUs) synthesized by the polycarboxyl ligands and metal atoms can produce directional polyatomic metal clusters. Then the secondary building units connected the nitrogen heterocyclic ligand as the co-ligands to construct fascinating porous inorganic-organic hybrid compounds. In addition, we also focus on the influence of different reaction conditions on the structure of the compound and look for the economical and efficient synthesis conditions. Then, we continue to explore the impact of porosity on the ability of adsorption of the compound and pay attention on the influence of metal clusters on the magnetism and optical properties. Finally, the aim of this thesis is to study the synthetic conditions and rules for these compounds and explore the relationships between structures and properties for the sets of compounds.

无机-有机杂化化合物是一类兼具无机物与有机物优点的材料,其在催化、吸附、光学和磁性材料等领域具有重要意义。用分子设计和晶体工程有关原理和方法，对无机-有机杂化化合物实现功能上的分子剪裁和分子组装，使之具有新颖结构和优良性能，是现代配位功能材料研究的发展趋势之一。其中，对具有多核金属簇基单元的无机-有机多孔杂化化合物的研究还很少。这主要是因为增大金属簇的核数以及可控设计合成规则的孔道结构都是研究的难点。本项目拟采用阴离子模板剂的方法来增大金属簇的核数，并选取与设计刚性羧酸配体与金属离子配位形成具有多核金属簇的次级结构单元,再利用有机含氮杂环配体可控合成具有规则孔道结构的无机-有机杂化化合物。研究不同的反应条件对所形成配合物结构的影响，寻找经济、高效的合成条件；探索配合物多孔特性的吸附能力、多核金属簇单元对磁性和发光性能的影响。 目的是探索新的合成方法、找出此类化合物的组装规律和构效关系。

无机-有机杂化化合物是一类兼具无机物与有机物优点的材料,它与传统的无机化合物不同之处在于金属离子或金属簇的存在可以为新材料带来各种物理化学性能，另外其多孔结构较高的比表面积、孔径及孔道环境的可调节性等特性又为材料带来了吸附、主客体识别等应用前景。 本项目系统选取具有不同骨架结构的多酸配体，通过阴离子模板剂诱导金属离子的聚集，并通过 “多核金属簇基单元”作为前躯体，连接具有特定功能的有机含氮杂环桥联配体，利用多种方法成功组装了多个系列的具有不同结构和性能的无机-有机杂化化合物。在考察和分析这些无机-有机杂化材料各种物化表征的基础上，对它们进行荧光客体分子识别、生物抗菌活性性能研究，获得了多例具有特殊吸附分离、荧光传感和良好抗菌性能的无机-有机杂化材料。重点研究了阴离子模板剂；有机配体的构型、长度；实验条件；多孔结构的孔道结构、稳定性、活化条件；金属离子释放等方面。并深入总结材料结构与功能的构效关系。本项目研究结果为具有多核金属簇单元的多孔有机-无机材料的设计与合成提供了实验和理论依据，丰富了多孔材料的种类，具有一定的系统性和创新性。