Abstract
The high-nuclearity polyoxothiomolybdate [H8Mo84S48O188(H2O)(12)(CH3COO)(24)](32-) has been prepared and characterized by single-crystal X-ray crystallography and H-1 NMK, IR, Raman, and UV-vis spectroscopy. The solid-state structure reveals, an unprecedented and intriguing arrangement consisting of a nanoscaled anionic cube. The surprisingly open structure of this {Mo-84}-type cubic box features a large inner void that is accessible via its six open square faces with diameters of ca. 9 angstrom. Importantly, this molecular system appears to be highly functionalizable because of the presence of 24 exposed exchangeable acetate ligands.