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

• Main Authors: Masooma Ibrahim, Eufemio Moreno-Pineda, Thomas Bergfeldt, Christopher E. Anson, Annie K. Powell
• Format: Article
• Language: English
• Published: MDPI AG 2018-01-01
• Series: Materials
• Subjects: heterometallic; 3d-4f polyoxometalate; molecular magnetism; luminescence; pomif; extended frameworks; trilacunary; wells-dawson polyanion; sandwich-type
• Online Access: http://www.mdpi.com/1996-1944/11/1/155

The reaction of [α-P2W15O56]12− with MnII and DyIII in an aqueous basic solution led to the isolation of an all inorganic heterometallic aggregate Na10(OH2)42[{Dy(H2O)6}2Mn4P4W30O112(H2O)2]·17H2O (Dy2Mn4-P2W15). Single-crystal X-ray diffraction revealed that Dy2Mn4-P2W15 crystallizes in the triclinic system with space group P 1 ¯ , and consists of a tetranuclear manganese(II)-substituted sandwich-type phosphotungstate [Mn4(H2O)2(P2W15O56)2]16− (Mn4-P2W15), Na, and DyIII cations. Compound Dy2Mn4-P2W15 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 Dy2Mn4-P2W15 and Mn4-P2W15 were studied. Also, magnetic properties were studied and compared with the magnetic behavior of [Mn4(H2O)2(P2W15O56)2]16−.