Synthesis, Crystal Structures, and Magnetic Properties of Three Novel Ferrocenecarboxylato-Bridged Lanthanide Dimers

Three novel ferrocenecarboxylato-bridged lanthanide dimers Gd2(mu 2-OOCFc)2(OOCFc)4(MeOH)2(H2O)2.2MeOH.2H2O (1) (Fc = (eta 5-C5H5)Fe(eta 5-C5H4)), Nd2(mu 2-OOCFc)2(OOCFc)4(H2O)4.2MeOH.H2O (2), and Y2(mu 2-OOCFc)2-(OOCFc)4(H2O)4.2MeOH (3) have been synthesized and characterized by single-crystal X-ray crystallography. In each complex, two Ln(III) (Ln = Gd, Nd, or Y) ions are bridged by two ferrocenecarboxylate anions as asymmetrically bridging ligands, leading to dimeric cores, Ln2(mu 2-OOCFc)2; each Ln(III) ion has an irregular polyhedral coordination environment with nine coordinated oxygen atoms derived from the ferrocenecarboxylate ligands and coordinated solvent molecules. In the solid-state structure of compound 1, Gd2(mu 2-OOCFc)2(OOCFc)4(MeOH)2(H2O)2 groups are joined together by hydrogen bonds forming a two-dimensional network. Both compounds 2 and 3 show one-dimensional chain structures by hydrogen bonding; they are different from 1. Magnetic measurements show unexpected ferromagnetic coupling between the gadolinium(III) ions; the best fittings to the experimental magnetic susceptibilities gave J = 0.006 cm-1 and g = 2.0 for 1. The magnetic behavior for 2 was also studied in the temperature range of 1.8-300 K.