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Magnetic Properties of Radical, Crystalline Mixed Cyclopentadienyl/Dithiolene Complexes

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Conducting and Magnetic Organometallic Molecular Materials

Part of the book series: Topics in Organometallic Chemistry ((TOPORGAN,volume 27))

Abstract

This chapter describes in detail a class of heteroleptic complexes associating cyclopentadienyl (Cp) and dithiolene (dt) ligands, essentially known with the Cp2M(dt), CpM(dt)2, [CpM(dt)]2 and CpM(dt) stoichiometries. The three first classes are reported with early transition metals (groups 4−7), while the latter is restricted to group 9 and 10 metal centers. Depending on the metal and the complex oxidation state, paramagnetic species can be isolated, as for example the formally d 1 species Cp2V(dt), [Cp2Mo(dt)]+ or [CpMo(dt)2], or the formally d 7 CpNi(dt). They all exhibit a rich structural chemistry and variable spin density distribution between Cp, M and dt fragments. Their magnetic properties in the solid state are a combination of an original spin density distribution and specific intermolecular interactions in the crystalline phase. They lead to a variety of behaviors, from independent spins with their associated Curie-type law, singlet-triplet systems and their extension to alternated spin chains and spin ladders, uniform spin chains or ordered antiferromagnetic ground states. Besides the S• • •S and S• • •M interactions which control most of the antiferromagnetic interactions observed so far in these magnetic organometallic complexes, the contribution of direct Cp• • •Cp and Cp• • •S interactions is shown to control in some cases the magnetic behavior of the complexes, an original feature in organometallic chemistry.

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Abbreviations

SOMO:

Singly occupied molecular orbital

TCNQ:

Tetracyanoquinodimethane

TMTSF:

Tetramethyltetraselenafulvalene

TTF:

Tetrathiafulvalene

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Acknowledgments

Our own contribution to this work has only been possible through an intense and long lasting collaboration with Dr R. Clérac and Prof C. Coulon from the Centre de Recherches Paul Pascal (CRPP-CNRS) in Bordeaux (France). Their strong involvement and exceptional knowledge of molecular magnetism were much appreciated. We also thank Drs T. Cauchy and M. Nomura for their invaluable contribution on the [CpNi(dt)] complexes and specially Dr Cauchy for careful reading of the manuscript.

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  1. Sciences Chimiques de Rennes, Université Rennes 1 and CNRS UMR 6226, Campus de Beaulieu, 35042, Rennes, France

    Marc Fourmigué

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  1. Marc Fourmigué
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Correspondence to Marc Fourmigué .

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Editors and Affiliations

  1. UMR CNRS 6226, Université de Rennes 1, Rennes CX, 35042, France

    Marc Fourmigué

  2. UMR 6226 CNRS, Université de Rennes 1, av. du Général Leclerc 263, Rennes CX, 35042, France

    Lahcène Ouahab

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Fourmigué, M. (2009). Magnetic Properties of Radical, Crystalline Mixed Cyclopentadienyl/Dithiolene Complexes. In: Fourmigué, M., Ouahab, L. (eds) Conducting and Magnetic Organometallic Molecular Materials. Topics in Organometallic Chemistry, vol 27. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-00408-7_7

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