A Trinuclear Zr‐Substituted Decanuclear Hetero‐Metal Sandwich Tungstoantimonate: Synthesis, Structure and Properties

Abstract

A new trinuclear Zr4+ cluster substituted decanuclear hetero‐metal sandwich tungstoantimonate aggregate [H2N(CH3)2]7Na3H5{[Zr3(OAc)W7(H2O)O25][B‐α‐SbW9O33]2}·22H2O (1) has been synthesized under hydrothermal condition by reacting [B‐α‐SbW9O33]9– precursor, ZrOCl2·8H2O, Na2WO4·2H2O and dimethylamine hydrochloride in sodium acetate buffer (pH = 4.8) and structurally characterized by elemental analyses, IR spectrum, thermogravimetric analysis (TGA), powder X‐ray diffraction (PXRD) and single‐crystal X‐ray diffraction. The structure unit of 1 consists of a new sandwich tungstoantimonate (TA) unit {[Zr3(OAc)W7(H2O)O25][B‐α‐SbW9O33]2}15– constituted by two trivacant Keggin [B‐α‐SbW9O33]9– fragments linked through an unseen hetero‐metal cluster [Zr3(OAc)W7(H2O)O25]3+. In addition, the polyoxoanion can also be described as two trivacant Keggin [B‐α‐SbW9O33]9– fragments and one divacant Lindqvist [W4O16]8– linked by a hexanuclear hetero‐metal cluster [Zr3(OAc)W3(H2O)O9]11+ link. Moreover, the solid‐state electrochemistry and electrocatalytic performances of 1 have been measured in 0.5 mol L–1 Na2SO4 + H2SO4 aqueous solution, and the results show that 1 illustrates comparatively apparent catalytic activities toward the BrO3– and H2O2 reduction.