Polyoxotungstate Archetype {P4W27} and its 3d Derivatives

The propensity of the new, phenylphosphonate-stabilized polyoxotungstate (C₆H₅P^VO)₂P₄W₂₄O₉₂]^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 {P₄W₂₇}, isolated as salts of the polyanions Na?{Mn^II(H₂O)}{WO(H₂O)}P₄W₂₆O₉₈]^13? ( 1 ) and K?{Cu^II(H₂O)}{W(OH)(H₂O)}P₄W₂₇O₉₉]^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).