Abstract

We report three-dimensional (3D) cyanido-bridged Mn–Nb and Co–Nb bimetal assemblies, MnII2[NbIV(CN)8]·(L)2·nH2O (1: L=5-aminopyrimidine, n=5; 2: L=5-methylpyrimidine, n=4), and CoII2[NbIV(CN)8] (4-pyridinealdoxime)8·2H2O (3). The single-crystal X-ray structural analyses show that 1 and 2 consist of isomorphic 3D cyanido-bridged network (monoclinic, P21/n) composed of square antiprism Nb sites and distorted octahedral Mn sites. Both 1 and 2 show ferrimagnetism with Curie temperatures (TC) of 32 and 34K, respectively, which is caused by the antiferromagnetic superexchange interaction between MnII (S=5/2) and NbIV (S=1/2) through the CN groups. 3 has a 3D cyanido-bridged network (tetragonal, I41/a) composed of a dodecahedral Nb site and axially distorted pseudo-octahedral Co site. This compound shows ferromagnetic ordering with a TC of 18K. Magnetization versus rotation angle of single crystal reveals that 3 has a large coercive field of 15000Oe as crystal is oriented to a-axis, which is due to the strong magnetic anisotropy on distorted CoII.

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