Trisubstituted 4f- and 4d tungstoantimonates as artificial phosphoesterases for nerve agent degradation

Abstract

Three new trisubstituted 4f- and 4d tungstoantimonates (TA) K₃Na₂₁[(M(CH₃COO))₃(HPO₃)(WO₄)(SbW₉O₃₃)₃]·nH₂O {M₃(HPO₃)Sb₃W₂₈} (M = Gd^III, Y^III, Yb^III, n = 35–36) were synthesized using a double-template synthetic approach. Following their characterization in the solid state employing single- and powder X-ray diffraction (XRD), IR-spectroscopy, and elemental – and thermogravimetric analyses (TGA), {M₃(HPO₃)Sb₃W₂₈} were subjected to a comprehensive set of solution characterization methods including UV/vis- and multinuclear ³¹P and ¹³C NMR spectroscopy. All representatives were shown to be highly active, recyclable, and stable Lewis-acid catalysts towards the nerve agent simulant O,O-dimethyl O-(4-nitrophenyl) phosphate (DMNP) at neutral pH (in Tris–HCl [125 mM] at pD 7.0 25 °C). Control experiments showing catalytic activity of the unsubstituted trilacunary TA [SbW₉O₃₃]⁹⁻ suggest the non-innocence of Tris in the DMNP hydrolysis for the first time.