Solvent-Induced Assembly of Octacyanometalates-Based Coordination Polymers with Unique afm1 Topology and Magnetic Properties

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-MV(CN)8MnII2(H2O)2(CH3OH)][NO3]}n (M = W 1, Mo 2), while polymer {[μ4-WV(CN)8MnII2(DMF)8](ClO4)}n (DMF = N,N-dimethylformamide) (3) was crystallized from the reaction of (Bu3NH)3[W(CN)8] and Mn(ClO4)2·6H2O in DMF. All three CPs 1, 2, and 3 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 1 and 2 crystallize in the monoclinic crystal system with space group of C2/c and possess the infinite 3D framework in an unprecedented afm1 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 3 crystallizes in the space group of P42/m as a 3D supermolecule structure, which is constructed by one-di...