Magneto-structural correlations in binuclear copper(II) compounds bridged by a ferrocenecarboxylato(-1) and an hydroxo- or methoxo-ligands

The syntheses, characterization and X-ray crystal structures of the first two examples of asymmetrically bridged dinuclear copper(II) complexes containing a ferrocenecarboxylato ligand and a methoxo group in [{Cu(dmen)}(2)(mu-OMe){mu-O2C(eta(5)-C5H4) Fe(eta(5)-C5H5)}] (ClO4)(2), 1, (dmen = N,N-dimethylethylenediamine) or an hydroxo group in [{Cu(tmen)}(2)(mu-OH){mu-O2C(eta(5)-C5H4) Fe(eta(5)-C5H5)}] (ClO4)(2), 2, (tmen = N,N,N'N'-tetramethylethylenediamine) are reported. Magneto-chemical studies revealed that 1 and 2 exhibit opposite superexchange interactions between the two Cu(II) paramagnetic centers: an antiferromagnetic coupling (J =- 11 cm- 1) in 1 and a ferromagnetic interaction (J = +29 cm(-1)) in 2. The results obtained from these studies suggest that the weak interactions between the Cu( II) ions and the perchlorate anions detected in the crystal structures are important to introduce significant distortions in the heterobridged [Cu-2(mu-OR){mu-O2C(eta 5-C5H4)Fe(eta(5)-C5H5)}](2+) cores of 1 and 2, which clearly affect the nature and strength of the superexchange interactions. Computational studies based on density functional theory and ab initio multicon. gurational second-order perturbation theory (CASPT2) calculations have also been performed in order to rationalize the magnetic behaviour of 1 and 2. The magneto-structural correlations for complexes containing the [Cu(mu-OR)(mu-O2CR')Cu] core are discussed, and the relevance of the out-of-plane angle of the R group with the Cu(mu-OR) Cu plane established.