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Issue 24, 2013
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Magnetic anisotropy and exchange coupling in a family of isostructural FeIII2LnIII2 complexes

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Abstract

The reaction of [Fe3O(O2CPh)6(H2O)3](O2CPh) with lanthanide/rare earth nitrate salts in the presence of triethanolamine (H3tea) in acetonitrile/methanol solution yields a series of compounds with isostructural tetranuclear core motifs [FeIII2LnIII23-OH)2(teaH)2(O2CCPh)6]·3MeCN (Ln = Ce (1), Pr (2), Nd (3), Sm (4), Eu (5), Gd (6), Tb (7), Dy (8), Ho (9), Er (10), Tm (11), Yb (12), Y (13)). In all cases the core topology is a defect-dicubane planar or “butterfly” Fe2Ln2 motif. Compounds 1–13 were investigated using a combination of experimental techniques and theoretical studies. Magnetic susceptibility measurements were carried out on all compounds. The magnetic coupling between the two FeIII centres is antiferromagnetic, with JFeFeca. −6.71(4) cm−1, while the Fe–Ln couplings are much weaker, e.g. JFeGd = 0.18(1) cm−1. Compounds 6, 7, 8 and 13 were selected for Mössbauer studies in order to investigate the influence of isotropic (GdIII), highly anisotropic non-Kramers and Kramers (TbIII and DyIII) and diamagnetic (YIII) rare earth ions on the local environment of the FeIII centres. Compounds 3, 6, 8 and 13 were also studied using X-Band EPR spectroscopy. For 13, with the diamagnetic YIII ion, this made it possible to obtain the D, E, JFeFe and g parameters for the iron centres. It is shown that the low-temperature spectra of compounds 3, 6 and 8 are determined by magnetic properties of rare-earth ions and the dipole–dipole interactions between the LnIII ions. The Fe–Ln interactions were confirmed as very weak and dipolar in nature by the temperature dependence of EPR spectra at T > 20 K.

Graphical abstract: Magnetic anisotropy and exchange coupling in a family of isostructural FeIII2LnIII2 complexes

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Publication details

The article was received on 11 Jan 2013, accepted on 28 Mar 2013 and first published on 28 Mar 2013


Article type: Paper
DOI: 10.1039/C3DT00105A
Citation: Dalton Trans., 2013,42, 8926-8938
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    Magnetic anisotropy and exchange coupling in a family of isostructural FeIII2LnIII2 complexes

    A. Baniodeh, Y. Lan, G. Novitchi, V. Mereacre, A. Sukhanov, M. Ferbinteanu, V. Voronkova, C. E. Anson and A. K. Powell, Dalton Trans., 2013, 42, 8926
    DOI: 10.1039/C3DT00105A

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