[ASAP] Sequential Isomerization of a Macrocyclic Polyoxometalate Archetype

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Controlled isomerization of individual {α-P2W12O48} polyoxotungstate building blocks under the constricted conditions of the macrocyclic [P8W48O184]40–archetype ({P8W48}) is linked to site-specific CuII coordination. The derivatives [αγαγ-P8W48O184{Cu(H2O)}2]36– (1), [γγγγ-P8W48O184{Cu(H2O)0.5}4]32– (2), and [αγγγ-P8W48O184{Cu(H2O)}3]34– (3) feature the {αγαγ-P8W48} and the hitherto unknown {γγγγ-P8W48} and {αγγγ-P8W48} isomers based on {α-P2W12} and/or CuII-stabilized {γ-P2W12} units and form from the reactions of the classical {P8W48} (={αααα-P8W48}) and CuCl2 in sodium acetate medium (pH 5.2). All products were thoroughly characterized in both the solid state and aqueous solutions, including electrocatalysis assessments.

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