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

文献信息

发布日期 2012-02-22

DOI 10.1039/C2CP23845D

影响因子 3.676

作者

Esther Coulaud, Denis Hagebaum-Reignier, Didier Siri, Paul Tordo, Nicolas Ferré

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摘要

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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来源期刊

Physical Chemistry Chemical Physics

CiteScore: 5.5

自引率: 10.3%

年发文量: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.