Magnetic properties of Cu(II) bischelate complexes with 3-imidazoline nitroxides. 2. Anab initio analysis of exchange interaction mechanisms |
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Authors: | R. N. Musin I. V. Ovcharenko L. Ohrström P. Rey |
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Affiliation: | 1. Institute of Chemical Kinetics and Combustion, Siberian Branch, Russian Academy of Sciences, USSR 2. Chalmers Technological University, G?theburg, Sweden 3. Nuclear Research Center, Grenoble, France
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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 Jcu-L and JL-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 JCu-L >JL -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. Translated fromZhurnal Strukturnoi Khimii, Vol. 38, No. 5, pp. 850–856, September-October, 1997. |
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