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Magnetic exchange coupling in bis-nitroxides: a theoretical analysis of the solvent effects

Abstract : Magnetic properties of nitroxide radicals can be greatly affected by solvent effects. In this study, the change of the magnetic exchange interaction J, coupling the two unpaired electrons of a model solvated antiferromagnetic bis-iminyl-nitroxide molecule (2IN), is rationalized thanks to different geometric and electronic criteria provided by density functional theory calculations. It is shown that for a given geometry, simple tools can be used to analyze with good accuracy the dependence of J with the solvent polarity. Estimates of two important magnetic parameters are given: the magnetic orbitals exchange and the in-site energy gap between ionic and neutral configurations. 2IN can be engaged in different hydrogen-bonds with first shell water molecules, modifying both the 2IN geometry and the electrostatic potential felt by the molecule. In all, the additivity of electrostatic and hydrogen-bond solvent effects is found to be responsible for J variations as large as 50%.
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https://hal-amu.archives-ouvertes.fr/hal-01415193
Contributor : Didier Siri <>
Submitted on : Monday, December 12, 2016 - 6:50:09 PM
Last modification on : Monday, April 20, 2020 - 11:04:02 AM

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Esther Coulaud, Denis Hagebaum-Reignier, Didier Siri, Paul Tordo, Nicolas Ferré. Magnetic exchange coupling in bis-nitroxides: a theoretical analysis of the solvent effects. Physical Chemistry Chemical Physics, Royal Society of Chemistry, 2012, 14 (16), pp.5504--5511. ⟨10.1039/c2cp23845d⟩. ⟨hal-01415193⟩

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