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

Masooma Ibrahim; Eufemio Moreno-Pineda; Thomas Bergfeldt; Christopher E Anson; Annie K Powell

doi:10.3390/ma11010155

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

Materials (Basel). 2018 Jan 17;11(1):155. doi: 10.3390/ma11010155.

Authors

Masooma Ibrahim¹, Eufemio Moreno-Pineda², Thomas Bergfeldt³, Christopher E Anson⁴, Annie K Powell^{5

6}

Affiliations

¹ Institute of Nanotechnology (INT), Karlsruhe Institute of Technology (KIT), Postfach 3640, 76021 Karlsruhe, Germany. masooma.ibrahim@kit.edu.
² Institute of Nanotechnology (INT), Karlsruhe Institute of Technology (KIT), Postfach 3640, 76021 Karlsruhe, Germany. eufemio.pineda@kit.edu.
³ Institute for Applied Materials (IAM-AWP), Karlsruhe Institute of Technology (KIT), Postfach 3640, 76021 Karlsruhe, Germany. thomas.bergfeldt@kit.edu.
⁴ Institute of Inorganic Chemistry, Karlsruhe Institute of Technology (KIT), Engesserstrasse 15, 76131 Karlsruhe, Germany. christopher.anson@kit.edu.
⁵ Institute of Nanotechnology (INT), Karlsruhe Institute of Technology (KIT), Postfach 3640, 76021 Karlsruhe, Germany. annie.powell@kit.edu.
⁶ Institute of Inorganic Chemistry, Karlsruhe Institute of Technology (KIT), Engesserstrasse 15, 76131 Karlsruhe, Germany. annie.powell@kit.edu.

Abstract

The reaction of [α-P₂W₁₅O₅₆]^12- with Mn^II and Dy^III 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 Dy^III 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-.

Keywords: 3d-4f polyoxometalate; extended frameworks; heterometallic; luminescence; molecular magnetism; pomif; sandwich-type; trilacunary; wells-dawson polyanion.