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

Three manganese–molybdenum/tungsten bimetallic coordination polymers, two 2D {{[μ 4 ‐M(CN) 8 ] 2 [Mn(dmf) 3 ] 2 [Mn(dmf) 4 ]} · 2DMF} n (M = W 1 , Mo 2 ) and a 1D {{[μ 4 ‐Mo(CN) 8 ][Mn(dmf) 4 ] 2 } · (ClO 4 )} n ( 3 ), were constructed from the reaction of the (Bu 3 NH) 3 [M(CN) 8 ] (M = W, Mo) and Mn(ClO 4 ) 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 P 2 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 P 4 2 / 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.