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π-Electron Magnetism pp 93–128Cite as

Magnetic Properties of Thiazyl Radicals

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

Abstract

A series of thiazyl radicals related to the trithiadiazolylium radical cation, S3N +•2 are described. In many instances the compounds exist as spin-paired singlets which are consequently diamagnetic. However, when the dimerisation process can be inhibited, these open shell molecules exhibit very strong exchange interactions, characterised by Weiss constants, θ, up to 102 K. Magneto-structural correlations show that, in the majority of instances, the magnetic exchange interactions are propagated via close intermolecular S···N and S···S contacts (typically in the region 3.1–3.7 Å). Examples of thiazyl radicals exhibiting magnetic ordering temperatures in excess of 50 K are described. In addition, the phenomenon of bistability (in which both open-shell monomeric and closed-shell dimeric forms are stable over the same temperature range) is discussed and examples of thiazyl radicals exhibiting bistability up to room temperature described.

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Authors and Affiliations

  1. Department of Chemistry, The University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, UK

    Jeremy M. Rawson

  2. Instituto de Materiales de Aragon, CSIC-Universidad de Zaragoza, 30009, Zaragoza, Spain

    Fernando Palacio

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  1. Jeremy M. Rawson
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  2. Fernando Palacio
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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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Rawson, J.M., Palacio, F. (2001). Magnetic Properties of Thiazyl Radicals. 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_4

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  • DOI: https://doi.org/10.1007/3-540-44684-2_4

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