Magnetism of Cyano-Bridged Ln3+−M3+Complexes. Part II:  One-Dimensional Complexes (Ln3+= Eu, Tb, Dy, Ho, Er, Tm; M3+= Fe or Co) with bpy as Blocking Ligand

The reaction of Ln(NO3)3(aq) with K3[Fe(CN)6] or K3[Co(CN)6] and 2,2'-bipyridine in water/ethanol led to 13 one-dimensional complexes: trans-[M(CN)4(mu-CN)2Ln(H2O)4(bpy)]n.4nH2O.1.5nbpy (Ln = Eu3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Lu3+; M = Fe3+, Co3+). The structures for [EuFe]n (1), [TbFe]n (2), [DyFe]n (3), [HoFe]n (4), [ErFe]n (5), [TmFe]n (6), [LuFe]n (7), [EuCo]n (8), [TbCo]n (9), [DyCo]n (10), [HoCo]n (11), [ErCo]n (12), and [TmCo]n (13) have been solved: they crystallize in the triclinic space group P and are isomorphous. They exhibit a supramolecular architecture created by the interplay of coordinative, hydrogen bonding, and pi-pi interactions. A stereochemical study of the eight-vertex polyhedra of the lanthanide ions, based on continuous shape measures, is presented. The Ln3+-Fe3+ interaction is antiferromagnetic in [DyFe]n and [TbFe]n. For [EuFe]n, [HoFe]n, [ErFe]n, and [TmFe]n, there is no sign of any significant interaction. The magnetic behavior of [DyFe]n suggests the onset of weak long-range ferromagnetic ordering at 2.5 K.