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 SM ISO690:2012COSTES, Jean-Pierre, DUHAYON, Carine, MALLET-LADEIRA, Sonia, SHOVA, Sergiu, VENDIER, Laure. Does the Sign of the Cu-Gd Magnetic Interaction Depend on the Number of Atoms in the Bridge? In: Chemistry - A European Journal, 2016, vol. 22, pp. 2171-2180. ISSN 0947-6539. DOI: https://doi.org/10.1002/chem.201504238 |
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  Chemistry - A European Journal |
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| Volumul 22 / 2016 / ISSN 0947-6539 | ||||||
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| DOI:https://doi.org/10.1002/chem.201504238 | ||||||
| Pag. 2171-2180 | ||||||
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Several theoretical investigations with CASSCF methods confirm that the magnetic behavior of Cu-Gd complexes can only be reproduced if the 5d Gd orbitals are included in the active space. These orbitals, expected to be unoccupied, do present a low spin density, which is mainly due to a spin polarization effect. This theory is strengthened by the experimental results reported herein. We demonstrate that Cu-Gd complexes characterized by Cu-Gd interactions through single-oxygen and three-atom bridges consisting of oxygen, carbon, and nitrogen atoms, present weak ferromagnetic exchange interactions, whereas complexes with bridges made of two atoms, such as the nitrogen-oxygen oximato bridge, are subject to weak antiferromagnetic exchange interactions. Therefore, a bridge with an odd number of atoms induces a weak ferromagnetic exchange interaction, whereas a bridge with an even number of atoms supports a weak antiferromagnetic exchange interaction, as observed in pure organic compounds and also, as in this case, in metal-organic compounds with an active spin polarization effect. |
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| Cuvinte-cheie coordination chemistry, Cu-Gd complexes, magnetic properties, Spin polarization, Structure elucidation |
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