School of Chemistry, University of Dublin, Trinity College, Dublin 2, Ireland.
CRANN Nanotechnology Institute &AMBER, Centre University of Dublin, Trinity College, Dublin 2, Ireland.
Nat Commun. 2017 May 9;8:15268. doi: 10.1038/ncomms15268.
Pioneered by Lehn, Cram, Peterson and Breslow, supramolecular chemistry concepts have evolved providing fundamental knowledge of the relationships between the structures and reactivities of organized molecules. A particular fascinating class of metallo-supramolecular molecules are hollow coordination cages that provide cavities of molecular dimensions promoting applications in diverse areas including catalysis, enzyme mimetics and material science. Here we report the synthesis of coordination cages with exceptional cross-sectional diameters that are composed of multiple sub-cages providing numerous distinctive binding sites through labile coordination solvent molecules. The building principles, involving Archimedean and Platonic bodies, renders these supramolecular keplerates as a class of cages whose composition and topological aspects compare to characteristics of edge-transitive {Cu} MOFs with AX stoichiometry. The nature of the cavities in these double-shell metal-organic polyhedra and their inner/outer binding sites provide perspectives for post-synthetic functionalizations, separations and catalysis. Transmission electron microscopy studies demonstrate that single molecules are experimentally accessible.
超分子化学概念由 Lehn、Cram、Peterson 和 Breslow 开创，为组织分子的结构和反应性之间的关系提供了基本的知识。一类特别引人入胜的金属超分子分子是中空配位笼，它们提供分子尺寸的空腔，促进了包括催化、酶模拟物和材料科学在内的多个领域的应用。在这里，我们报告了具有特殊横截面直径的配位笼的合成，这些配位笼由多个亚笼组成，通过不稳定的配位溶剂分子提供了众多独特的结合位点。构建原则涉及阿基米德和柏拉图立体，使这些超分子 Keplerates 成为一类笼状结构，其组成和拓扑方面与具有 AX 化学计量比的边缘转移 {Cu} MOF 的特征相媲美。这些双壳层金属有机多面体中的空腔的性质及其内外结合位点为后合成功能化、分离和催化提供了前景。透射电子显微镜研究表明，实验上可以获得单个分子。
