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A new tetra-Zr(IV)-substituted polyoxotungstate aggregate

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Abstract

A new tetra-Zr-substituted tungstophosphate (TP), [H2N(CH3)2]6Na6H8{Zr2[SbP2W4(OH)2O21][α2-PW10O38]}2·50H2O (1), has been made by the hydrothermal reaction of the [B-α-SbW9O33]9− building block with Zr4+ cations and PO43− anions in the presence of dimethylamine hydrochloride and NaOAc–HOAc (pH = 4.8), and further characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD), 31P NMR spectroscopy and single-crystal X-ray diffraction. 1 is a toroidal structure formed by two divacant [α2-PW10O38]11− units and two [SbP2W4(OH)2O21]7− fragments linked by four Zr4+ cations. Note that the TP is reassembled with tetrahedral PO4 replacing the triangular pyramidal SbO3 in the [B-α-SbW9O33]9− precursor. In addition, the pendant SbO3 derives from the dissociation of the [B-α-SbW9O33]9− precursor. Furthermore, the electrochemical properties of 1 have been studied in Na2SO4 + H2SO4 supporting electrolyte (0.5 mol L−1), and indicate that 1 exhibits apparent catalytic activity toward H2O2 and BrO3 reduction. The 31P NMR spectrum of 1 exhibits three signals with approximately proportional intensities, which is consistent with the solid-state structure.

Graphical abstract: A new tetra-Zr(iv)-substituted polyoxotungstate aggregate

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Publication details

The article was received on 14 Aug 2018, accepted on 06 Sep 2018 and first published on 08 Sep 2018


Article type: Paper
DOI: 10.1039/C8DT03317J
Citation: Dalton Trans., 2018, Advance Article
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    A new tetra-Zr(IV)-substituted polyoxotungstate aggregate

    H. Li, Y. Wang, Z. Zhang, B. Yang and G. Yang, Dalton Trans., 2018, Advance Article , DOI: 10.1039/C8DT03317J

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