Solvent-Induced Assembly of Octacyanometalates-Based Coordination Polymers with Unique <i>afm</i>1 Topology and Magnetic Properties

Abstract

Aqueous solution was introduced into the self-assembly of water-insoluble (Bu₃NH)₃[M­(CN)₈] (M = W, Mo) and Mn­(NO₃)₂·6H₂O to afford two, three-dimensional (3D) coordination polymers (CPs), {[μ₈-M^V(CN)₈Mn^II₂(H₂O)₂(CH₃OH)]­[NO₃]}_<i>n</i> (M = W <b>1</b>, Mo <b>2</b>), while polymer {[μ₄-W^V(CN)₈Mn^II₂(DMF)₈]­(ClO₄)}_<i>n</i> (DMF = <i>N</i>,<i>N</i>-dimethylformamide) (<b>3</b>) was crystallized from the reaction of (Bu₃NH)₃[W­(CN)₈] and Mn­(ClO₄)₂·6H₂O in DMF. All three CPs <b>1</b>, <b>2</b>, and <b>3</b> have been well-characterized by elemental analysis, infrared spectra, single-crystal X-ray diffraction, as well as thermogravimetric analysis. The single-crystal X-ray structural analysis shows that both CPs <b>1</b> and <b>2</b> crystallize in the monoclinic crystal system with space group of <i>C</i>2/<i>c</i> and possess the infinite 3D framework in an unprecedented <i>afm</i>1 topology geometry, which is an unreported 4-nodal 4,4,8,8-coordinated net with point symbol {4¹¹.6¹².8⁵}­{4¹⁷.6¹⁰.8}­{4⁵.6}₄. Polymer <b>3</b> crystallizes in the space group of <i>P</i>4₂/<i>m</i> as a 3D supermolecule structure, which is constructed by one-dimensional (1D) cationic {[μ₄-W^V(CN)₈Mn^II₂(DMF)₈]⁺}_<i>n</i> chains linked via the hydrogen bonds. Magnetic susceptibility measurements in the temperature range of 2–300 K reveal that CPs <b>1</b> and <b>2</b> exhibit the similar typical antiferromagnetic properties, while CP <b>3</b> shows the ferromagnetic property