Heterometallic 3d–4f cluster-containing polyoxotungstate obtained by partial disassembly of preformed large clusters†
Abstract
A new heterometallic 3d–4f cluster-containing polyoxotungstate KNa5{K2Dy2Cu2(H2O)8(SbW9O33)2}·17H2O (1) was designed and synthesized by reaction of the preformed large cluster [N(CH3)4]10Na12[Na2Sb8W36O132(H2O)4]·26H2O ({Sb8W36}), transition-metal (TM) and Ln3+ cations. Compound 1 is the first 3d–4f heterometallic cluster-containing sandwich-type tungstoantimonite obtained by partial decomposition of a preformed large cluster. Further, the sandwich-type polyoxoanion combines with two additional 4p cations resulting in a ring-like 3d–4f–4p cluster {K2Dy2Cu2(H2O)8}-containing polyoxotungstate. The sandwich polyoxoanion {K2Dy2Cu2(H2O)8(SbW9O33)2} was structurally similar to the well-known anion {K3Cu3(H2O)10(SbW9O33)2}, in which one alkali metal cation and one TM cation were both replaced by the rare earth metal cations. Furthermore, the 3d–4f–4p cluster-containing polyoxoanions were bridged by the K+ ion located at their central metal belt into a one-dimensional (1D) wavelike chain. An electrochemical study revealed that compound 1 exhibited electrocatalytic activity for reduction of the NO2− and O2, and a direct 4-electron electrochemical reduction process of O2 was achieved in 1-containing aqueous solution.
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