Synthesis, Structures, and Magnetic Properties of a Series of Cyano-Bridged Fe−Mn Bimetallic Complexes

The preparation and crystal structures of five cyano-bridged Fe−Mn complexes, [(bipy)2FeII(CN)2MnII(bipy)2]2(ClO4)4
(1), [(bipy)2FeII(CN)2MnII(DMF)3(H2O)]2(ClO4)4 (2), {[(Tp)FeIII(CN)3]2MnII(DMF)2(H2O)}2 (3), {[(Tp)FeIII(CN)3]2MnII(DMF)2}n (4), and Na2[MnIIFeII(CN)6] (5) (bipy = 2,2‘-bipyridine, Tp = tris(pyrazolyl)hydroborate), are reported
here. Compounds 1−4 contain the basic Fe2(CN)4Mn2 square building units, of which 1−3 show the motif of discrete
molecular squares of Fe2(CN)4Mn2 and 4 possesses a 1D double-zigzag chainlike structure, while compound 5 is
a 3D cubic framework analogous to that of Prussian blue. Compounds 1 and 2 show weak ferromagnetic interactions
between two Mn(II) ions through the bent −NC−Fe(II)−CN− bridges. Compound 3 shows weak antiferromagnetic
coupling between the Fe(III) and Mn(II) ions, while compound 4 displays a metamagnetic-like behavior with TN =
5.2 K and Hc = 10.5 kOe. Compound 5 exhibits a ferromagnetic ordering with Tc = 3.5 K, coercive field, Hc, =
330 G, and a remnant magnetization of 503 cm3 Oe mol-1.