title: Microscopic origins of the ferromagnetic exchange coupling in oxoverdazyl-based Cu(II) complex.
abstract: The exchange channels governing the experimentally reported coupling constant (J(expt)=6 cm(-1)) value in the verdazyl-ligand based Cu(II) complex [Cu(hfac)(2)(imvdz)] are inspected using wave function-based difference dedicated configuration interaction calculations. The interaction between the two spin 1/2 holders is summed up in a unique coupling constant J. Nevertheless, by gradually increasing the level of calculation, different mechanisms of interaction are turned on step by step. In the present system, the calculated exchange interaction then appears alternatively ferromagnetic/antiferromagnetic/ferromagnetic. Our analysis demonstrates the tremendously importance of some specific exchange mechanisms. It is actually shown that both parts of the imvdz ligand simultaneously influence the ferromagnetic behavior which ultimately reaches J(calc)=6.3 cm(-1), in very good agreement with the experimental value. In accordance with the alternation of J, it is shown that the nature of the magnetic behavior results from competing channels. First, an antiferromagnetic contribution can be essentially attributed to single excitations involving the pi network localized on the verdazyl part. In contrast, the sigma ligand-to-metal charge transfer (LMCT) involving the imidazole moiety affords a ferromagnetic contribution. The distinct nature sigma/pi of the mechanisms is responsible for the net ferromagnetic behavior. The intuitively innocent part of the verdazyl-based ligands is deeply reconsidered and opens new routes into the rational design of magnetic objects.
authors.affiliation: Laboratoire de Chimie, Ecole Normale Supérieure de Lyon, CNRS, Université de Lyon, Lyon, France.
authors.forename: Jean-Baptiste
authors.initials: JB
authors.lastname: Rota
authors.forename: Carmen J
authors.initials: CJ
authors.lastname: Calzado
authors.forename: Cyrille
authors.initials: C
authors.lastname: Train
authors.forename: Vincent
authors.initials: V
authors.lastname: Robert
mesh_terms: D003198:Computer Simulation; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D006571:Heterocyclic Compounds / Q000737:chemistry*; D008024:Ligands; D008280:Magnetics; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: D006571:Heterocyclic Compounds; D008024:Ligands; D009942:Organometallic Compounds; D003300:Copper