基于磁性簇基元后合成修饰组装簇基MOFs及其溶液组装行为研究

A special class of cluster−organic frameworks is combining the structural features and functionality of both polynuclear coordination clusters and metal–organic frameworks (MOFs), two families of crystalline molecular materials. It has attracted widespread attention in recent years, for their intriguing potential applications in gas absorption, heterogeneous catalysis and magnetic materials, etc. However, the controllable assembly and functional optimization starting from cluster units is still a difficult point in the field of assembly chemistry. This project intends to design and synthesize serial polynuclear complexes with free functional groups (such as -NH2, -OH, -CHO, -CN, etc.) and potential active site (coordinately unsaturated metal ions, ligands, anions, etc). Using them as building units, the organic/inorganic post-synthetic modification and hierarchical assembly behaviors will be studied through post-synthesis organic reaction, anion-exchange expansion, bridging ligands, etc. The solution behavior (such as stability, ion exchange, abundance variation, ligand substitution) and solution mechanism will be studied by using Mass spectrometry technique. Exploring the difference in magneto-structural relationship and optimizing the mechanism of magnetic super-exchange interaction in the assembly, this project want to provide valuable information for the design and preparation of complicated magnetic cluster-based polymer crystalline materials.

金属-有机框架材料（MOFs）与多核簇基配合物是晶态分子基材料的两大分支，潜在应用于气体吸附、非均相催化、磁性材料等多个领域，而结合了它们结构及功能特点的簇基MOFs，近年来更是受到了广泛关注，但基于簇基元的反应性实现簇基MOFs的可控组装及性能调控，仍然是当前组装化学的研究重难点之一。本课题拟合成系列含自由官能团（氨基、羟基、醛基、氰基等）磁性簇基元配合物，并根据簇基元结构特征，利用其潜在组装位点（自由官能团、配位不饱和的中心金属离子、配体、阴离子等），通过有机后合成反应、阴阳离子交换拓展及引入拓展配体等方式，开展系列有机/无机后合成修饰及阶段性组装行为研究。利用质谱技术研究各基元溶液行为（稳定性、丰度变化、离子交换、配体取代等）及溶液组装机理等。研究修饰组装前后物种的差异性磁构关系，探讨磁性超交换作用优化机制，为复杂磁性簇基元聚集体晶态材料的结构设计和可控制备提供有价值的依据。

项目主要探讨了①基于{Co14}簇基元前驱体开展系列后合成修饰及阶段性组装行为研究；②系列复杂簇基配合物的阶段性组装及溶液组装行为研究；③系列簇基MOFs的修饰行为及其催化性能研究；④系列簇基配合物及MOFs的无机-有机双驱动原位构建策略研究等工作。重点研究了基于{Co14}前驱体构建复杂{Co11Cd6}，{Co12Cd12}，{Co13Cd6}等的修饰组装过程、差异性磁构关系及有机催化性能；系列{Fe5}、{Mn38}、{Tb12}、{Co12Mo24}、{Zn54}复杂簇基MOFs及簇基聚集体的溶液自组装；{Ni3}和{Co3}簇基MOFs的后修饰及电催化性能；端基Co盐修饰的簇基MOFs及其有机催化性能研究；通过原位组装系列Dy分子簇，Co分子笼探讨共价配位双驱动组装策略。为功能分子基材料的结构设计和可控制备提供有价值的依据。本项目取得了预期进展，完成了合同约定的目标任务。迄今为止，项目研究成果以论文形式发表在 ACS Catal.; J. Mater. Chem. A; Chem. Commun.; Inorg. Chem. Front.; Inorg. Chem.; Dalton Trans.; Cryst. Growth & Des.等SCI学术刊物上发表学术论文28篇，其中影响因子大于4.0 的一共有18篇，3篇被选为封面文章。授权发明专利2项。项目期间培养博士2名，硕士11名。