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Issue 7, 2016
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First coordination compounds based on a bis(imino nitroxide) biradical and 4f metal ions: synthesis, crystal structures and magnetic properties

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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

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Publication details

The article was received on 12 Nov 2015, accepted on 22 Dec 2015 and first published on 23 Dec 2015


Article type: Paper
DOI: 10.1039/C5DT04469C
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Citation: Dalton Trans., 2016,45, 2936-2944
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    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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