Magnetic properties of Cu(II) bischelate complexes with 3-imidazoline nitroxides. 2. Anab initio analysis of exchange interaction mechanisms

Abstract

The mechanism responsible for the emergence of ferromagnetic exchange interactions in bischelate complexes of Cu²⁺ with enaminoketone derivatives of 3-imidazoline nitroxide CuL₂ is studied by ab initio quantum chemical methods. The parameters J_cu-L and J_L-L’ of exchange interactions between the unpaired electrons of the paramagnetic centers (Cu²⁺ ion and N-O groups of nitroxyl ligands L and L’) of these complexes were calculated in terms of the full 3x3 configuration interaction between the singlet states constructed in a basis set of molecular orbitals of unpaired electrons. It is shown that for variations of the structure of the coordination polyhedron around the Cu²⁺ ion from square planar to tetrahedral the exchange interactions between the unpaired electrons of the paramagnetic centers is ferromagnetic J_Cu-L >J_L -L’>0, which agrees with the data of magnetic measurements. The principal mechanism of exchange interactions in CuL₂ complexes is the delocalization mechanism that is due to a minor transfer of spin density from the 3d-orbitals of Cu²⁺ to the Σ-orbitals of the N-O groups of L and L’ ligands.