Synthesis and Characterization of a Heterometallic Extended Architecture Based on a Manganese(II)-Substituted Sandwich-Type Polyoxotungstate

The reaction of [α-P(2)W(15)O(56)](12−) with Mn(II) and Dy(III) in an aqueous basic solution led to the isolation of an all inorganic heterometallic aggregate Na(10)(OH(2))(42)[{Dy(H(2)O)(6)}(2)Mn(4)P(4)W(30)O(112)(H(2)O)(2)]·17H(2)O (Dy(2)Mn(4)-P(2)W(15)). Single-crystal X-ray diffraction revealed that Dy(2)Mn(4)-P(2)W(15) crystallizes in the triclinic system with space group P [Formula: see text] , and consists of a tetranuclear manganese(II)-substituted sandwich-type phosphotungstate [Mn(4)(H(2)O)(2)(P(2)W(15)O(56))(2)](16−) (Mn(4)-P(2)W(15)), Na, and Dy(III) cations. Compound Dy(2)Mn(4)-P(2)W(15) exhibits a 1D ladder-like chain structure based on sandwich-type segments and dysprosium cations as linkers, which are further connected into a three-dimensional open framework by sodium cations. The title compound was structurally and compositionally characterized in solid state by single-crystal XRD, powder X-ray diffraction (PXRD), Fourier-transform infrared spectroscopy (FTIR), thermogravimetric (TGA), and elemental analyses. Further, the absorption and emission electronic spectra in aqueous solutions of Dy(2)Mn(4)-P(2)W(15) and Mn(4)-P(2)W(15) were studied. Also, magnetic properties were studied and compared with the magnetic behavior of [Mn(4)(H(2)O)(2)(P(2)W(15)O(56))(2)](16−).