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

• Published in: Inorganic chemistry Vol. 55; no. 17; pp. 9006 - 9011
• Main Authors: Guo, Ling-Yu, Zeng, Su-Yuan, Jagličić, Zvonko, Hu, Qi-Dong, Wang, Shi-Xuan, Wang, Zhi, Sun, Di
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 06.09.2016
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/acs.inorgchem.6b01468

A planar hexanuclear cobalt ring was clamped by two bivacant α1-[PW10O37]9– with the assistance of the pyridazine bridges to form a novel sandwiched Co­(II)-polyoxometalate cluster compound, [Na­(H2O)6]­[Co3(OH) (pydz)4(H2O)7]­[Co6(PW10O37)2(pydz)4(H2O)6]·43H2O (1; 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 1 comprises a hexahydrated sodium, a trinuclear [Co3(OH) (pydz)4(H2O)7]5+ cationic cluster, and an anionic [Co6(PW10O37)2­(pydz)4(H2O)6]6– sandwiched cluster, thus giving an intrinsical intercluster compound. The isolation of such cluster was dependent on the in situ transformation of trivacant [α-P2W15O56]12– to α1-[PW10O37]9– under the hydrothermal condition. The CV shows reversible multielectron waves from the redox of WVI in 1. Cluster 1 exhibits remarkable electrocatalytic activity toward the reduction of nitrite. Magnetism studies indicated a weak anti-ferromagnetic exchange interaction between Co­(II) ions within 1.