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Ising-type Magnetic Anisotropy and Slow Relaxation of the Magnetization in Four-Coordinate Amido-Pyridine FeII Complexes

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posted on 26.10.2016, 18:18 by C. Gunnar Werncke, Mohammed-Amine Bouammali, Julie Baumard, Nicolas Suaud, Cyril Martins, Nathalie Guihéry, Laure Vendier, Jianxia Zheng, Jean-Baptiste Sortais, Christophe Darcel, Sylviane Sabo-Etienne, Jean-Pascal Sutter, Sébastien Bontemps, Céline Pichon
A family of four-coordinate FeII complexes formed with N,N′-chelating amido-pyridine ligands was synthesized, and their magnetic properties were investigated. These distorted tetrahedral complexes exhibit significant magnetic anisotropy with zero-field splitting parameter D ranging between −17 and −12 cm–1. Ab initio calculations enabled identification of the structural factors that control the nature of the magnetic anisotropy and the rationalization of the variation of D in these complexes. It is shown that a reduced N–Fe–N angle involving the chelating nitrogen atoms of the ligands is at the origin of the negative D value and that the torsion between the two N–Fe–N planes imposed by steric hindrances further increases the |D| value. Field-induced slow relaxation of magnetization was observed for the three compounds, and a single-molecule magnet behavior with an energy barrier for magnetization flipping (Ueff) of 27 cm–1 could be evidenced for one of them.

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