10.1021/acs.inorgchem.6b01468.s002

A Pyridazine-Bridged Sandwiched Cluster Incorporating Planar Hexanuclear Cobalt Ring and Bivacant Phosphotungstate

Abstract

A planar hexanuclear cobalt ring was clamped by two bivacant α<sub>1</sub>-[PW<sub>10</sub>O<sub>37</sub>]<sup>9–</sup> with the assistance of the pyridazine bridges to form a novel sandwiched Co­(II)-polyoxometalate cluster compound, [Na­(H<sub>2</sub>O)<sub>6</sub>]­[Co<sub>3</sub>(OH) (pydz)<sub>4</sub>(H<sub>2</sub>O)<sub>7</sub>]­[Co<sub>6</sub>(PW<sub>10</sub>O<sub>37</sub>)<sub>2</sub>(pydz)<sub>4</sub>(H<sub>2</sub>O)<sub>6</sub>]·43H<sub>2</sub>O (<b>1</b>; pydz = pyridazine).This cluster was identified by X-ray single-crystal diffraction, elemental analysis, Fourier transform IR and UV–visible spectroscopies, and cyclic voltammetry (CV). Structural analysis reveals that <b>1</b> comprises a hexahydrated sodium, a trinuclear [Co<sub>3</sub>(OH) (pydz)<sub>4</sub>(H<sub>2</sub>O)<sub>7</sub>]<sup>5+</sup> cationic cluster, and an anionic [Co<sub>6</sub>(PW<sub>10</sub>O<sub>37</sub>)<sub>2</sub>­(pydz)<sub>4</sub>(H<sub>2</sub>O)<sub>6</sub>]<sup>6–</sup> sandwiched cluster, thus giving an intrinsical intercluster compound. The isolation of such cluster was dependent on the in situ transformation of trivacant [α-P<sub>2</sub>W<sub>15</sub>O<sub>56</sub>]<sup>12–</sup> to α<sub>1</sub>-[PW<sub>10</sub>O<sub>37</sub>]<sup>9–</sup> under the hydrothermal condition. The CV shows reversible multielectron waves from the redox of W<sup>VI</sup> in <b>1</b>. Cluster <b>1</b> exhibits remarkable electrocatalytic activity toward the reduction of nitrite. Magnetism studies indicated a weak anti-ferromagnetic exchange interaction between Co­(II) ions within <b>1</b>

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oai:figshare.com:article/3749382Last time updated on 2/12/2018

This paper was published in FigShare.

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