Issue 7, 2016

First coordination compounds based on a bis(imino nitroxide) biradical and 4f metal ions: synthesis, crystal structures and magnetic properties

Abstract

The synthesis, crystal structures and magnetic properties of two families of heterospin complexes containing lanthanide ions and a bis(imino nitroxide) biradical (IPhIN = 1-iodo-3,5-bis(4′,4′,5′,5′-tetramethyl-4′,5′-dihydro-1H-imidazole-1′-oxyl)benzene) are reported: in [Ln2(hfac)6(IPhIN)(H2O)2] compounds, two lanthanide ions [Ln = GdIII (1) and DyIII (2)] are coordinated to the biradical, and in [Ln(hfac)3(IPhIN)(H2O)] compounds, one lanthanide ion (Ln = TbIII (3), GdIII (4) or DyIII (5)) is coordinated to the biradical. Ferromagnetic intramolecular magnetic interactions between GdIII and the biradical were found for 1 and 4, while intramolecular magnetic interactions between the radicals were ferro- and antiferromagnetic, respectively. Compound 2 shows a field induced slow relaxation of magnetization, which (under an external applied field of 2 kOe) exhibits an activation energy barrier of ΔE/kB = 27 K and a pre-exponential factor of 1.4 × 10−8 s. To support the magnetic characterization of compound 3ab initio calculations were also performed.

Graphical abstract: First coordination compounds based on a bis(imino nitroxide) biradical and 4f metal ions: synthesis, crystal structures and magnetic properties

Supplementary files

Article information

Article type
Paper
Submitted
12 Nov 2015
Accepted
22 Dec 2015
First published
23 Dec 2015

Dalton Trans., 2016,45, 2936-2944

Author version available

First coordination compounds based on a bis(imino nitroxide) biradical and 4f metal ions: synthesis, crystal structures and magnetic properties

S. G. Reis, M. Briganti, D. O. T. A. Martins, H. Akpinar, S. Calancea, G. P. Guedes, S. Soriano, M. Andruh, R. A. A. Cassaro, P. M. Lahti, F. Totti and M. G. F. Vaz, Dalton Trans., 2016, 45, 2936 DOI: 10.1039/C5DT04469C

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