pH-Controlled assembly of two novel Dawson-sandwiched clusters involving the in situ reorganization of trivacant α-[P2W15O56](12-) into divacant α-[P2W16O57](8.)

Modified classical trivacant Wells-Dawson α-[P2W15O56](12-) and the assembly of related sandwiched transition metal clusters are of interest, but surprisingly few reports of these materials exist because of the sensitivity of α-[P2W15O56](12-) to the assembly environment. Herein, we describe the pH-controlled assembly of two novel Dawson-sandwiched clusters, (H2bpz)6[Co2(P2W16O57)2]·22H2O (1, bpz = 3,3',5,5'-tetramethyl-4,4'-bipyrazole) and (H2bpz)6[Co3H2(P2W16O57)(P2W15O56)(H2O)]·12H2O (2), involving the in situ transformation of α-[P2W15O56](12-). Both clusters were characterized by X-ray single-crystal diffraction, FT-IR spectroscopy, UV-Visible spectroscopy, thermogravimetric analysis, powder X-ray diffraction, and elemental analyses. X-ray crystallography showed that both heteropolytungstates become divacant α-[P2W16O57](8-) and symmetrically encapsulate two edge-shared CoO6 octahedra in the interior in 1, while only one divacant α-[P2W16O57](8-) is observed in 2, which combined with another trivacant α-[P2W15O56](12-) to asymmetrically clamp three edge-shared CoO6 octahedra. The α-[P2W16O57](8-) heteropolytungstate should be generated in situ from α-[P2W15O56](12-)via self-decomposition equilibria in solution. Their electrochemical behaviors reveal characteristic multi-electron redox processes related to W(VI) centers. The electrocatalytic reduction performances toward nitrite, hydrogen peroxide, chlorate, bromate and iodate were fully measured and discussed; among these species, both clusters exhibit the best electrocatalytic activity towards the reduction of bromate. Magnetic measurements indicate weak ferromagnetic exchange interactions between Co atoms sandwiched by vacant polyoxometalates.