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9-Cobalt(II)-Containing 27-Tungsto-3-germanate(IV): Synthesis, Structure, Computational Modeling, and Heterogeneous Water Oxidation Catalysis

Haider, A.; Bassil, B. S.; Soriano-López, J.; Qasim, H. M.; Sáenz de Pipaón, C.; Ibrahim, M.; Dutta, D.; Koo, Y. S.; Carbó, J. J.; Poblet, J. M.; Galán-Mascarós, J. R.; Kortz, U.
Inorg. Chem. 2019, 58 (17), 11308-11316, DOI: 10.1021/acs.inorgchem.9b01495.

The 9-cobalt(II)-containing trimeric, cyclic polyanion [Co9(OH)3(H2O)6(PO4)2(B-α-GeW9O34)3]21– (1) was synthesized in an aqueous phosphate solution at pH 8 and isolated as a hydrated mixed sodium–cesium salt. Polyanion 1 was structurally and compositionally characterized in the solid state by single-crystal X-ray diffraction, Fourier transform infrared spectroscopy, as well as thermogravimetric and elemental analyses. The magnetic and electrochemical properties of 1 were also studied and compared with those of its phosphorus analogue, [Co9(OH)3(H2O)6(HPO4)2(B-α-PW9O34)3]16– (Co9-P). The electrochemical water oxidation activity of the cesium salt of 1 under heterogeneous conditions was also studied and shown to be superior to that of Co9-P. The experimental results were supported by computational studies.