Crystal Chemistry and SAXS Studies of an Octahedral Polyoxoarsenotungstate Nanocluster Encapsulating Four Unprecedented Thorium Arsenate Fragments (Th3As2On – n = 25 or 26)

Dufaye, Maxime; Duval, Sylvain; Stoclet, Grégory; Loiseau, Thierry

European Journal of Inorganic Chemistry, 2019, vol 2019, 42, pp. 4500-4505

DOI:10.1002/ejic.201900732

Abstract

The reaction of [H-B-?-AsVW9O34]8– with the 5f tetravalent thorium cation in presence of an acetate buffer and KCl at pH = 4.7 gives rise to the formation of an octahedral polyoxoarsenotungstate nanocluster [K4Th3(H2O)3AsO(µ2-O)32Th3(H2O)2AsO(µ2-O)323(AsW10O38)6]38–. This molecule is constructed around four unprecedented Th3As2On (n = 25 or 26) fragments stabilized by the presence of six arsenotungstates AsVW10O38 coming from the partial decomposition of the polyanionic AsVW9O34 precursor. This molecular architecture was characterized by single-crystal X-ray diffraction and its solution behavior was evaluated by using small angle X-ray scattering (SAXS) analyses. It shows that the molecule decomposes to form smaller 1:2 sandwich like polyanionic entities.

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