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The Mechanism of the Through-Space Magnetic Interactions in Purely Organic Molecular Magnets

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π-Electron Magnetism

Part of the book series: Structure and Bonding ((STRUCTURE,volume 100))

Abstract

The mechanism of the intermolecular magnetic (or through-space) interactions found in purely organic molecular crystals is reviewed, using results from the ab initio studies of model systems, and from the statistical analysis of the packing of nitronyl nitroxide crystals presenting dominant ferro or antiferromagnetic interactions. First of all, the foundations of the McConnell-I mechanism (more properly called a proposal) are reviewed from a rigorous theoretical point of view. It is shown that this proposal lacks a rigorous foundation and works in some prototype systems due to error compensations associated to the high symmetry of the model systems employed to evaluate such a mechanism. It will be shown how the McConnell-I mechanism fails in rationalizing the magnetic properties of well known nitronyl nitroxide crystals. We will also show the existence of pitfalls in many of the magneto-structural correlations employed today. One example of an erroneous correlation is that which associates the magnetic character of a nitronyl nitroxide dimer with the relative orientation of the ONCNO groups in these two molecules. Consequently, new magneto-structural relationships are needed based on unbiased assumptions. For such a purpose, we need to have solid data on the properties of the through-space magnetic interactions at the microscopic level. We will review in the last sections the current knowledge about these properties, obtained from ab initio computations and crystal packing studies.

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Authors and Affiliations

  1. Departament de Química Física, Facultat de Química and CER Química Teòrica, Universitat de Barcelona, Av. Diagonal 647, 08028, Barcelona, Spain

    Juan J. Novoa & Mercè Deumal

Authors
  1. Juan J. Novoa
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  2. Mercè Deumal
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Editors and Affiliations

  1. Institut de Ciència de Materials de Barcelona, Campus Universitari de Bellaterra, 01893, Cerdanyola, Spain

    Jaume Veciana

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© 2001 Springer-Verlag Berlin Heidelberg

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Novoa, J.J., Deumal, M. (2001). The Mechanism of the Through-Space Magnetic Interactions in Purely Organic Molecular Magnets. In: Veciana, J., et al. π-Electron Magnetism. Structure and Bonding, vol 100. Springer, Berlin, Heidelberg. https://doi.org/10.1007/3-540-44684-2_2

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  • DOI: https://doi.org/10.1007/3-540-44684-2_2

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  • Publisher Name: Springer, Berlin, Heidelberg

  • Print ISBN: 978-3-540-41680-7

  • Online ISBN: 978-3-540-44684-2

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