MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-Sen University, Guangzhou 510275, China.
Department of Chemistry and Pharmacy, Friedrich-Alexander University Erlangen-Nuremberg, 91058 Erlangen, Germany.
J Am Chem Soc. 2020 Apr 22;142(16):7283-7288. doi: 10.1021/jacs.0c01035. Epub 2020 Apr 9.
Coordination geometries of transition metals play vital roles in the self-assembly process of supramolecular coordination complexes. Herein, seven-coordinate 3d metal ions were applied as templates and catalytically active sites for subcomponent self-assembly that resulted in a new category of covalent metallacycles. Single-crystal structures showed that the sizes, configurations, and functionalization of covalent metallacycles could be tuned by the selection of rigid dihydrazide, transition metal ions, and prefunctionalized subcomponents, respectively. Moreover, metallacycles decorated with carboxylic groups could be employed as precursors to prepare aerogels through hierarchical self-assembly, which also exhibited high catalytic activity for cycloaddition of CO into cyclic carbonates.
过渡金属的配位几何在超分子配位配合物的自组装过程中起着至关重要的作用。在此，七配位 3d 金属离子被用作模板和催化活性位点，用于亚组分的自组装，从而产生了一类新的共价金属环。单晶结构表明，共价金属环的尺寸、构型和功能化可以分别通过选择刚性二酰肼、过渡金属离子和预官能化的亚组分来调节。此外，带有羧基的金属环可以作为前体通过分级自组装来制备气凝胶，其对 CO 环加成到环状碳酸酯的催化活性也很高。
