Synthesis and characterization of organotriphosphonate-functionalized TM-containing polyoxotungstates

Abstract

A new family of organotriphosphonate-functionalized TM-containing polyoxotungstates, K₄H₆[H₄{(AsW₉O₃₃)TM(H₂O)W₅O₁₁(N(CH₂PO₃)₃)}₂(μ₂-O)₂]·24H₂O [TM = Ni (1), Co (2), Mn (3)], have been synthesized from the preformed POM precursor [As₂W₁₉O₆₇(H₂O)]¹⁴⁻. They were thoroughly characterized by single crystal X-ray diffraction, IR and UV spectra, thermogravimetric (TG), X-ray powder diffraction (XRPD), X-ray photoelectron spectroscopy (XPS) and elemental analyses. The structures are comprised of two Wells–Dawson building blocks in opposite directions that are connected by two μ₂-oxo groups acting as a “hinge”, with the two ATMP ligands serving as a stanchion. The electrochemical behavior of these compounds has also been investigated.