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Title: Single-molecule magnet behavior of a tetranuclear iron(III) complex. The origin of slow magnetic relaxation in iron(III) clusters
Authors: Barra, A. L.
Caneschi, A.
Cornia, A.
Fabrizi De Biani, Fabrizia 
Gatteschi, D.
Sangregorio, C.
Sessoli, R.
Sorace, L.
Issue Date: 1999
Project: None 
The synthesis, crystal structure, and magnetic characterization of a novel tetranuclear iron(III) methoxo-bridged cluster of formula Fe4(OCH3)6(dpm)6 (where Hdpm = dipivaloylmethane) is reported. The cluster has a ground spin state of S = 5, which is selectively populated below 20 K. High-field EPR spectra revealed that the system has a uniaxial magnetic anisotropy, corresponding to a zero field splitting parameter D = −0.2 cm-1 of the S = 5. Such anisotropy below 1 K gives rise to the slow relaxation of the magnetization similar to that of super-paramagnets. To investigate the origin of the magnetic anisotropy we have evaluated the projection of the single-ion and dipolar contributions to the zfs of the ground state. The zfs tensors of the three structurally independent iron(III) centers have been calculated from the coordination geometry and spectroscopic data using the angular overlap model. To test the reliability of the approach high-field EPR spectra of the parent monomer Fe(dpm)3 have been recorded to compare the calculated and experimental zfs parameters.
ISSN: 0002-7863
DOI: 10.1021/ja9818755
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