Structure; magnetic properties; Mossbauer spectroscopy
Abstract :
[en] The reaction of N-methydiethanolamine (mdeaH2), benzoic acid, FeCl3, and Ln(NO3)3·6H2O or LnCl3·xH2O yields a series of decanuclear coordination clusters, [Ln3Fe7(μ4-O)2(μ3OH)2(mdea)7(μ-benzoate)4(N3)6]·4MeCN·H2O, where Ln = Gd III (1)orTb III (2), and [Er 3Fe7(μ4-O)2(μ3-OH)2(mdea)7(μbenzoate)4(N3)5(MeOH)]Cl·7.5H2O·11.5MeOH (3). The isostructural compounds 1−3 all crystallize isotypically in the triclinic space group P1̅ with Z = 2, as does the previously reported dysprosium analogue 4. Six of the Fe III ions are pseudooctahedrally coordinated, whereas the seventh has a trigonal-bipyramidal coordination geometry. Temperature-dependent direct-current magnetic susceptibility studies indicate that intracluster antiferromagnetic interactions are dominant in 1−3. The frequency-dependent out-of-phase (χ′′) alternating-current susceptibility reveals that 2 undergoes a slow relaxation of its magnetization, presumably resulting from anisotropy of the Tb III ions. Between 30 and 295 K, the 57Fe Mö ssbauer spectra reveal paramagnetic behavior with six partially resolved quadrupole doublets, one for the trigonal-bipyramidal Fe III site and five for the six pseudooctahedral Fe III sites. The Mö ssbauer spectra of 2 and 3 obtained between 3 and 30 K are consistent with the presence of Fe III intracluster antiferromagnetic coupling with slow magnetic relaxation relative to the Larmor precession time. Further, the observed changes in the effective magnetic field values in the spectra measured at 3 K with increasing applied field are consistent with the effect of the local spin polarization along the applied magnetic field direction, a behavior reminiscent of antiparallel spin-coupled iron molecular paramagnetic systems.
Disciplines :
Chemistry
Author, co-author :
Abbas, Ghulam; Karlsruhe Institute of Technology > Inorganic Chemistry
Lan, Yanhua; Karlsruhe Institute of Technology > Inorganic Chemistry
Mereacre, Valeriu; Karlsruhe Institute of Technology > Inorganic Chemistry
Buth, Gernot; Karlsruhe Institute of Technology > Inorganic Chemistry
Sougrati, Moulay T.; University of Liege > Physics
Grandjean, Fernande ; Université de Liège - ULiège > Département de physique > Département de physique
Long, Gary J.; Missouri University of Science and Technology > Chemistry
Anson, CHristopher E; Karlsruhe Institute of Technology > Inorganic Chemistry
Powell, Annie K; Karlsruhe Institute of Technology > Inorganic Chemistry
Language :
English
Title :
Synthesis, Magnetism, and 57Fe Mössbauer Spectroscopic Study of a Family of [Ln3Fe7] Coordination Clusters (Ln = Gd, Tb, and Er),”
Publication date :
October 2013
Journal title :
Inorganic Chemistry
ISSN :
0020-1669
eISSN :
1520-510X
Publisher :
American Chemical Society, Washington, United States - District of Columbia
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