Tetranuclear [Co–Gd]2 Complexes: Aiming at a Better Understanding of the 3d-Gd Magnetic Interaction

Tetranuclear [Co–Gd]2 complexes were prepared by using trianionic ligands possessing amide, imine, and phenol functions. The structural determinations show that the starting cobalt complexes present square planar or square pyramid environments that are preserved in the final tetranuclear [Co–Gd]2 complexes. These geometrical modifications of the cobalt coordination spheres induce changes in the cobalt spin ground states, going from S = 1/2 in the square planar to S = 3/2 for the square pyramid environments. Depending on the ligand, the complexes display antiferromagnetic or ferromagnetic CoII–GdIII interactions. The temperature dependence of the magnetic susceptibility-temperature products indicate that the Co–Gd interaction is ferromagnetic when high spin Co ions are concerned and antiferromagnetic in the case of low spin Co ions. This different magnetic behavior can be explained if we observe that the singly occupied σ dx2–y2 orbital is populated (S = 3/2 Co ions) or unoccupied (S = 1/2 Co ions). Such an observation furnishes invaluable information for the understanding of the more general 3d-4f magnetic interactions.