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

Abstract

AbstractThree manganese–molybdenum/tungsten bimetallic coordination polymers, two 2D {{[μ4‐M(CN)8]2[Mn(dmf)3]2[Mn(dmf)4]}·2DMF}n (M = W 1, Mo 2) and a 1D {{[μ4‐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)2·6H2O 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 P21/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 {42·63·8}{42·6}. Compound 3 crystallizes in the tetragonal crystal system with the P42/m space group. All three compounds are further assembled into 3D supramolecular structures through intermolecular C–H···N or C–H···O 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.