Abstract
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 {Cu2} MOFs with A3X4 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.
Highlights
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
Preparative efforts were primarily directed towards the synthesis of new cage topologies with controllable inner cavities whose chemical, geometrical and electronic attributes can give rise to space-restricted properties that are exploitable in catalytic processes[5,6,17,18], for separations[19,20], drug delivery[21] and sensing[22,23]
At initial stages of the presented work we were interested in the rotational flexibility associated with the acetylene moiety of the m-BTEB ligand, which was expected to produce a number of isomeric coordination compounds[42]
Summary
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. The molecular species represent highly augmented MOP whose complexity and topological characteristics compare to key structural attributes of MOFs. While the conformational anti, anti-arrangement of two benzoate moieties of the m-BTEB ligand gives rise to a 120° binding geometry that promotes the formation of the outer shell, the rotational flexibility of the third alkyne-benzoate moiety promotes the formation of inner cages and allows the inner-located dinuclear {Cu2} complexes to adopt variable arrangements.
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