Hydrothermal Syntheses, Crystal Structures, And Magnetic Properties of a Series of Complexes Constructed from Multinuclear Copper Clusters and Polyoxometalates

A series of complexes constructed from multinuclear copper Clusters and polyoxometalates, namely. [Cu-6(PO4)(2)(H2O)(2)(bpy)(6)](H3O)(2)[P2W18O62](bpy=2,2'-bipyridine, 1), [Cu-6(PO4)(2)(H2O)(4)(phen)(6)](H2O)(2)[P2W18O62] (phen = 1,10-phenanthroline, 2), [Cu2Cl(phen)(4)][PW12O40] (3), [Cu-4(HPO4)(2)(H2O)(4)(phen)(4)](H3O)(2)[PV3W9O40] (4), and [Cu-4(HPO4)(2)(H2O)(2)(bpy)(4)](H2O)(2)[PVW11O40] (5), have been successfully synthesized in situ under hydrothermal conditions via changing the ligand, adjusting the pH value, and introducing low-valence metal (V5+). Complex 1 represents the first example of 1D linear chain constructed from alternating mixed-valence hexacopper (four Cu2+ and two Cu+) clusters and Wells-Dawson type polyoxometalates, Complex 2 exhibits an unprecedented 2D layer network based oil hexacopper phosphate and Wells-Dawson type polyoxometalates, Complex 3 constructed from dicopper coordination compounds and Keggin polyoxometalates, was obtained from the similar hydrothermal treatment of 2 at much lower pH value. Complexes 4-5 represent the first two examples of 1D linear chain constructed from alternating tetracopper phosphate cations and V5(+)-substituted Keggin type polyoxometalates. The magnetic properties of the complexes have been investigated between 2 and 300 K.