A Family of Polynuclear Clusters Containing Cyano-Bridged T-Shaped Fe<sup>III</sup><sub>3</sub>M<sup>II</sup> (M = Cu, Co, Mn) Metal Cores: Syntheses, Structures, and Magnetic Properties
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A new family of polynuclear clusters containing the FeIII3MII cores [(Tp4Bo)6Fe6(CN)18M2Na2(H2O)16]·4H2O (M = Cu, Co, Mn; 1−3) and [(Tp4Bo)6Fe6(CN)18M2Na2(H2O)12(DMF)4]·H2O (M = Cu, Co, Mn; 4−6) have been synthesized and structurally characterized. Complexes 1−3 crystallize in the P21/c space group, and 4−6 crystallize in the P21/n space group. All six complexes consist of two symmetry-related T-shaped [(Tp4Bo)3(CN)9Fe3M]− subunits linked by two Na+ cations. Each polynuclear cluster in 1−6 strongly interacts with 12 adjacent such units through π−π interactions, leading to the formation of 3D 12-connected frameworks. Magnetic studies show appreciable magnetic anisotropies in compounds 1, 2, 4, and 5. Antiferromagnetic interactions were observed in complexes 3 and 6.
