15-Copper(II)-containing 36-tungsto-4-silicates(IV) [Cu15O2(OH)10X(A-α-SiW9O34)4]25− (X = Cl, Br): synthesis, structure, magnetic properties, and electrocatalytic CO2 reduction

The 15-copper(II)-containing 36-tungsto-4-silicates [Cu15O2(OH)10X(A-α-SiW9O34)4]25− (X = Cl, 1; Br, 2) have been prepared in 70% yield by reaction of the trilacunary 9-tungstosilicate precursor [A-α-SiW9O34]10− with Cu2+ ions in aqueous pH 8 medium. Both polyanions 1 and 2 were isolated as hydrated mixed potassium/sodium salts and characterized in the solid state by FT-IR, TGA, single-crystal XRD, and elemental analysis. DC magnetic susceptibility measurements from 1.8–300 K established the ground state to be paramagnetic with a magnetic moment corresponding to 15 uncoupled Cu2+ (S = 1/2) ions. EPR measurements and simulations were consistent with this analysis. Electrochemical studies were performed for polyanions 1 and 2 dissolved in solution to elucidate the electroactivity of both copper and tungstate sites. Using 2 as a representative example, the electrocatalytic activity towards CO2 reduction upon deposition on a glassy carbon electrode surface, while retaining selectivity relative to hydrogen evolution, was demonstrated.