Supramolecular Assembly of Geometrically Unstable Hybrid Organic-Inorganic Uranyl Peroxide Cage Clusters and Their Transformations.

An aromatic ligand was introduced into the synthesis of a uranyl peroxide polyoxometalate formulated as K(UO)(O)(OH)(CHPO)·65HO that consists of a unique "open oyster" shaped structure (U) with intramolecular H-bonds. In the solid state, K-π and π-π interactions as well as K-O bonds enable the formation of a supramolecular network between U clusters. U adopts an incomplete fullerene topology and was utilized as a precursor from which the geometrically favored U structure was produced. A potassium-encapsulated U structure was obtained upon heating the solution containing U.