Polyoxotungstate Archetype {P4 W27 } and its 3d Derivatives

Abstract

The propensity of the new, phenylphosphonate-stabilized polyoxotungstate [(C₆ H₅ P^V O)₂ P₄ W₂₄ O₉₂ ]^16- to act as a precursor for new 3d metal-functionalized polyanions has been investigated. Reactions with Mn^II and Cu^II induce the formation of the previously unknown polyoxotungstate archetype {P₄ W₂₇ }, isolated as salts of the polyanions [Na⊂{Mn^II (H₂ O)}{WO(H₂ O)}P₄ W₂₆ O₉₈ ]^13- (1) and [K⊂{Cu^II (H₂ O)}{W(OH)(H₂ O)}P₄ W₂₇ O₉₉ ]^14- (2), which were characterized in the solid state (single-crystal X-ray diffraction, elemental and TG analyses, IR spectroscopy, SQUID magnetometry) and in aqueous solution (UV/Vis spectroscopy, cyclic voltammetry).

Keywords: Polyoxometalates; electrochemistry; magnetochemistry; single-crystal X-ray analysis.