External-Template-Assisted Formation of Octacyanometalate-Based MV-MnII (M = W, Mo) Bimetallic Coordination Polymers with Magnetic Properties

Three manganese-molybdenum/tungsten bimetallic coordination polymers, two 2D {{[(4)-M(CN)(8)](2)[Mn(dmf)(3)](2)[Mn(dmf)(4)]}2DMF}(n) (M = W 1, Mo 2) and a 1D {{[(4)-Mo(CN)(8)][Mn(dmf)(4)](2)}(ClO4)}(n) (3), were constructed from the reaction of the (Bu3NH)(3)[M(CN)(8)] (M = W, Mo) and Mn(ClO4)(2)6H(2)O molecular building blocks in DMF solvent in the presence (for 1 and 2) or absence (for 3) of the organic ligand bis(benzimidazol-2-yl)pyridine. Single-crystal X-ray diffraction structure analysis indicated that compounds 1 and 2 both crystallize in the monoclinic crystal system with the P2(1)/c space group and possess the same 2D network. The 2D layer structures of 1 and 2 have a (3,4)-connected 2-nodal topology with the point symbol {4(2)6(3)8}{4(2)6}. Compound 3 crystallizes in the tetragonal crystal system with the P4(2)/m space group. All three compounds are further assembled into 3D supramolecular structures through intermolecular C-HN or C-HO hydrogen bonds. The magnetic susceptibility of compounds 1 and 3 was investigated in the temperature range of 2-300 K; these compounds exhibit typical ferrimagnetic properties.