Hydrothermal reaction of a macrocyclic inorganic POM cavitand Li17(NH4)21H2[P8W48O184] with [Pt­(H2O)2(OH)4] results in coordination of up to six {Pt­(H2O) x (OH)4–x } fragments to the internal surface of the polyoxoanion. The product was isolated as K22(NH4)9H3[{Pt­(OH)3(H2O)}6P8W48O184]·79H2O (1) and characterized by multiple techniques in the solid state (SCXRD, XRPD, XPS, FTIR, and TGA) and in solution (NMR, ESI-MS, and HPLC-ICP-AES). Electrochemical properties were studied both in solution and as components of the paste electrode. The complex shows electrocatalytic activity in water oxidation.

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