single molecule magnet; class III mixed valence compound; Mössbauer spectroscopy
Abstract :
[en] The magnetic, electronic and Mössbauer spectral properties of [Fe2L(μ-OAc)2]ClO4, 1, where L is the dianion of the tetraimino-diphenolate macrocyclic ligand, H2L, indicate that 1 is a class III mixed valence iron(II/III) complex with an electron that is fully delocalized between two crystallographically inequivalent iron sites to yield a [Fe2]V cationic configuration with a St = 9/2 ground state. Fits of the dc magnetic susceptibility between 2 and 300 K and of the isofield variable-temperature magnetization of 1 yield an isotropic magnetic exchange parameter, J, of –32(2) cm–1 for an electron transfer parameter, B, of 950 cm–1, a zero-field uniaxial D9/2 parameter of –0.9(1) cm–1, and g = 1.95(5). In agreement with the presence of uniaxial magnetic anisotropy, ac susceptibility measurements reveal that 1 is a single-molecule magnet at low temperature with a single molecule magnetic effective relaxation barrier, Ueff, of 9.8 cm–1. At 5.25 K the Mössbauer spectra of 1 exhibit two spectral components, assigned to the two crystallographically inequivalent iron sites with a static effective hyperfine field; as the temperature increases from 7 to 310 K the spectra exhibit increasingly rapid relaxation of the hyperfine field on the iron-57 Larmor precession time of 5 × 10–8 s. A fit of the temperature dependence of the average effective hyperfine field yields |D9/2| = 0.9 cm–1. An Arrhenius plot of the logarithm of the relaxation frequency between 5 and 85 K yields a relaxation barrier of 17 cm–1.
Disciplines :
Chemistry
Author, co-author :
Hazra, Susanta; University of Calcutta > Chemistry
Sasmal, Sujit; University of Calcutta > Chemistry
Fleck, Michel; University of Vienna > Institute for Mineralogy and Crystallography
Grandjean, Fernande ; Université de Liège - ULiège > Département de physique > Département de physique
Sougrati, Moulay T.; University of Liege > Physics
Ghosh, Meenakshi; Max Planck Institut Bioanorganische CHemie
Harris, T David; Berkeley University of California - UC Berkeley > Chemistry
Bonville, Pierre; CEA Saclay > Physique de la Matiere Condensée
Long, Gary J; Missouri University of Science and Technology > Chemistry
Mohanta, Sasankasekhar; University of Calcutta > Chemistry
Language :
English
Title :
Slow Magnetic Relaxation and Electron Delocalization in an S = 9/2 Iron(II/III) Complex Featuring Two Crystallographically Inequivalent Iron Sites
Alternative titles :
[en] Relaxation magnétique lente et délocalisation électronique dans un complexe de fer(II/III) avec S=9/2 et deux sites cristallographiques inéquivalents
Publication date :
06 May 2011
Journal title :
Journal of Chemical Physics
ISSN :
0021-9606
eISSN :
1089-7690
Publisher :
American Institute of Physics, New York, United States - New York
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