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[TDNQ][CoCp*2] and [TDNQ]3[CoCp2]2; Radical Anions of a 1,2,5-Thiadiazolo-naphthoquinone

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Department of Chemistry, University of Guelph, Guelph, Ontario N1G 2W1, Canada
§ 185 Chelsea Avenue, London, Ontario N6J 3J5, Canada
# Laboratorium für Festkörperphysik, ETH Zürich, 8093 Zürich, Switzerland
CNRS, UPR 8641, Centre de Recherche Paul Pascal (CRPP), Equipe “Matériaux Moléculaires Magnétiques”, 115 avenue du Dr. Albert Schweitzer, Pessac, F-33600, France
Université de Bordeaux, UPR 8641, Pessac, F-33600, France
Cite this: Cryst. Growth Des. 2011, 11, 6, 2520–2527
Publication Date (Web):April 5, 2011
Copyright © 2011 American Chemical Society

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    Abstract Image

    The first crystal structure of a quinone[1,2,5]thiadiazole radical anion is presented. Reduction of naphtha[2,3-c][1,2,5]thiadiazole-4,9-dione (TDNQ) with outersphere electron transfer agents, decamethylcobaltocene (CoCp*2) and cobaltocene (CoCp2), by slow mixing of solutions, generates two species: [TDNQ][CoCp*2] and [TDNQ]3[CoCp2]2, respectively. The [TDNQ][CoCp*2] is soluble in a wide variety of organic solvents, whereas [TDNQ]3[CoCp2]2 is generally insoluble. The radical anion oxidation state, TDNQ•—, in [TDNQ][CoCp*2] is confirmed by lengthened C–O bond distances in the (solvated) crystal structure, as compared to neutral TDNQ, shifting of the ν(C–O) stretch in the IR absorption spectrum, and the presence of a solution electron paramagnetic resonance (EPR) signal. In the [TDNQ]3[CoCp2]2 species, copacking of single-molecule radical anions, TDNQ•—, and bimolecular radical anion units, (TDNQ)2•—, with cobaltocenium cations is observed. The magnetic measurements highlight the presence of dominating antiferromagnetic interactions between TDNQ•— and (TDNQ)2•— spins in this cobaltocene salt.

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    Table of isotropic Fermi contact couplings from computational studies. Spin density distribution from computation studies. Crystallographic experimental details. Crystallographic information files (CIF) for 2·3CH2Cl2 and 3. This material is available free of charge via the Internet at

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    Cited By

    This article is cited by 13 publications.

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    11. René T. Boeré. Inorganic and organometallic radicals of main group elements. 2012, 22-57.
    12. Marc Fourmigué. Organic π‐Radicals in the Solid‐State: From Localised to Delocalised σ‐Bonding. 2012, 143-162.
    13. N. P. Gritsan, A. V. Zibarev. Chalcogen-nitrogen π-heterocyclic radical anion salts: the synthesis and properties. Russian Chemical Bulletin 2011, 60 (11) , 2131-2140.

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