The propensity of the new, phenylphosphonate‐stabilized polyoxotungstate [(C6H5PVO)2P4W24O92]16− to act as a precursor for new 3d metal‐functionalized polyanions has been investigated. Reactions with MnII and CuII induce the formation of the previously unknown polyoxotungstate archetype {P4W27}, isolated as salts of the polyanions [Na⊂{MnII(H2O)}{WO(H2O)}P4W26O98]13− (1) and [K⊂{CuII(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).
Controlled isomerization of individual {α-P 2 W 12 O 48 } polyoxotungstate building blocks under the constricted conditions of the macrocyclic [P 8 W 48 O 184 ] 40− archetype ({P 8 W 48 }) is linked to site-specific Cu II coordination. The derivatives [αγαγ-P 8 W 48 O 184 {Cu(H 2 O)} 2 ] 36− (1), [γγγγ-P 8 W 48 O 184 {Cu(H 2 O) 0.5 } 4 ] 32− (2), and [αγγγ-P 8 W 48 O 184 {Cu-(H 2 O)} 3 ] 34− (3) feature the {αγαγ-P 8 W 48 } and the hitherto unknown {γγγγ-P 8 W 48 } and {αγγγ-P 8 W 48 } isomers based on {α-P 2 W 12 } and/or Cu IIstabilized {γ-P 2 W 12 } units and form from the reactions of the classical {P 8 W 48 } (={αααα-P 8 W 48 }) and CuCl 2 in sodium acetate medium (pH 5.2). All products were thoroughly characterized in both the solid state and aqueous solutions, including electrocatalysis assessments. Article pubs.acs.org/IC
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