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

Three new trisubstituted 4f- and 4d tungstoantimonates (TA) K(3)Na(21)[(M(CH(3)COO))(3)(HPO(3))(WO(4))(SbW(9)O(33))(3)]·nH(2)O {M(3)(HPO(3))Sb(3)W(28)} (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), {M(3)(HPO(3))Sb(3)W(28)} were subjected to a comprehensive set of solution characterization methods including UV/vis- and multinuclear (31)P and (13)C 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 [SbW(9)O(33)](9−) suggest the non-innocence of Tris in the DMNP hydrolysis for the first time.