Magnetism of the heteropolymetallic systems

Abstract

The field of heteropolymetallic systems with magnetic metal centers occupies a crossing point between biology and physics. For instance the Cu(II)-Fe(III) interaction in cytochrome oxidase is of the same nature as the Cu(II)-Mn(II) interaction in a novel system which could be the first molecular ferromagnet. The mechanism of the interaction is discussed, both from a phenomenological view point using a spin Hamiltonian, and from an orbital view point. An orbital model for the isotropic interaction is presented. It is based on the concept of natural magnetic orbitals. The mechanism of the anisotropic and antisymmetric interactions is more briefly treated. The role of the Zeeman perturbation is then considered in relation with the magnetic and EPR properties of the heterobimetallic complexes. Several examples are presented to emphasize that the nature, ferro- or antiferromagnetic of the isotropic interaction is controlled by the symmetry of the magnetic orbitals. The concept of overlap density is introduced. It permits an estimation of the magnitude of the ferromagnetic stabilization in the case of orthogonality of the magnetic orbitals. The Cu(II)-Fe(III) interaction, in relation to the situation encountered in cytochrome oxidase, the Cu(II)-Ni(II) interaction and a few additional selected examples are discussed. A section deals with the case where one of the interacting ions has an orbital degeneracy. Afterwards, the heterotrinuclear complexes are studied. The important concept of regular and irregular spin state structure is developped and the Mn(II)Cu(II)Mn(II) triad is presented as a spectacular example of irregular spin state structure. A section is devoted to the ordered bimetallic chains. The theory is presented, both at a qualitative and quantitative levels and the already reported compounds of this kind are discussed. One of them may be considered as one of the first molecular ferromagnets. The last but one section concerns the systems with even more subtle spin orders. In conclusion, the vast perspectives of this area are outlined.