Cyano-Bridged Hexanuclear Fe4M2 (M = Ni, Co, Mn) Clusters:  Spin-Canted Antiferromagnetic Ordering of Fe4Ni2 Cluster

Heterobimetallic hexanuclear cyano-bridged complexes, [{Fe(Tp)(CN)3}4{M(MeCN)(H2O)2}2]·10H2O·2MeCN [M = Ni (1), Co (2), Mn (3); Tp = hydrotris(1-pyrazolyl)borate], have been synthesized in H2O−MeCN solution. Complexes 1 − 3 are isostructural and hexanuclear with [{Fe(Tp)(CN)3}4{M(MeCN)(H2O)2}2] units linked by hydrogen bonds to form a 2D-structure in the solid state. Complex 1 is a canted antiferromagnet that undergoes a field-induced spin-flop-like transition at ∼1 T and 2 K. At 4.45 K 1 has a transition to paramagnetic state of noninteracting S = 4 magnetic clusters. However, 2 and 3 show antiferromagnetic intracluster coupling. Facile loss of solvent from 2 alters the local symmetry resulting in changing the intracluster interaction from antiferro- to ferromagnetic.