Synthesis, Magnetism, and 57Fe Mössbauer Spectroscopic Study of a Family of [Ln3Fe7] Coordination Clusters (Ln = Gd, Tb, and Er),”

Abbas, Ghulam; Lan, Yanhua; Mereacre, Valeriu; Buth, Gernot; Sougrati, Moulay T.; Grandjean, Fernande; Long, Gary J.; Anson, CHristopher E; Powell, Annie K

doi:10.1021/ic401011d

Article (Scientific journals)

Synthesis, Magnetism, and 57Fe Mössbauer Spectroscopic Study of a Family of [Ln3Fe7] Coordination Clusters (Ln = Gd, Tb, and Er),”

Abbas, Ghulam; Lan, Yanhua; Mereacre, Valeriu et al.

2013 • In Inorganic Chemistry, 52, p. 11767

Peer Reviewed verified by ORBi

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https://hdl.handle.net/2268/169676

DOI
10.1021/ic401011d

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24089701

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Keywords :

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

Volume :

Pages :

11767

Peer reviewed :

Peer Reviewed verified by ORBi

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since 28 June 2014

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