Tetradecanuclear Iron(III)-Oxo Nanoclusters Stabilized by Trilacunary Heteropolyanions

The tetrameric, multi-Fe^III-containing polyoxotungstates [Fe₁₄O₆(OH)₁₃­(P₂W₁₅O₅₆)₄]^31– (<b>1</b>) and [Na₂Fe₁₄(OH)₁₂­(PO₄)₄(<i>A</i>-α-XW₉O₃₄)₄]^20– (X = Si^IV (<b>2</b>), Ge^IV (<b>3</b>)) have been successfully synthesized under conventional reaction conditions in aqueous, slightly acidic (<b>1</b>), or basic (<b>2</b> and <b>3</b>) media. Polyanions <b>1-3</b> were characterized in the solid state by single-crystal X-ray diffraction, IR spectroscopy, thermogravimetric analysis, and magnetic studies, and in solution by electrochemistry