ACS Publications. Most Trusted. Most Cited. Most Read
My Activity
CONTENT TYPES

Figure 1Loading Img

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

View Author Information
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
https://doi.org/10.1021/cg2002783
Copyright © 2011 American Chemical Society

    Article Views

    713

    Altmetric

    -

    Citations

    LEARN ABOUT THESE METRICS
    Other access options
    Supporting Info (3)»

    Abstract

    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.

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. You can change your affiliated institution below.

    Supporting Information

    ARTICLE SECTIONS
    Jump To

    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 http://pubs.acs.org.

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    This article is cited by 13 publications.

    1. Valentina Milašinović, Anna Krawczuk, Krešimir Molčanov, Biserka Kojić-Prodić. Two-Electron Multicenter Bonding (‘Pancake Bonding’) in Dimers of 5,6-Dichloro-2,3-dicyanosemiquinone (DDQ) Radical Anions. Crystal Growth & Design 2020, 20 (8) , 5435-5443. https://doi.org/10.1021/acs.cgd.0c00658
    2. Nikolay A. Pushkarevsky, Nikolay A. Semenov, Alexey A. Dmitriev, Natalia V. Kuratieva, Artem S. Bogomyakov, Irina G. Irtegova, Nadezhda V. Vasilieva, Bela E. Bode, Nina P. Gritsan, Lidia S. Konstantinova, J. Derek Woollins, Oleg A. Rakitin, Sergey N. Konchenko, Victor I. Ovcharenko, and Andrey V. Zibarev . Synthesis and Properties of the Heterospin (S1 = S2 = 1/2) Radical-Ion Salt Bis(mesitylene)molybdenum(I) [1,2,5]Thiadiazolo[3,4-c][1,2,5]thiadiazolidyl. Inorganic Chemistry 2015, 54 (14) , 7007-7013. https://doi.org/10.1021/acs.inorgchem.5b01033
    3. Andrey V. Zibarev. Chalcogen–Nitrogen Heterocyclic Radicals. 2023, 168-186. https://doi.org/10.1039/BK9781839167386-00168
    4. Markus Rohdenburg, Vladimir A. Azov, Jonas Warneke. New Perspectives in the Noble Gas Chemistry Opened by Electrophilic Anions. Frontiers in Chemistry 2020, 8 https://doi.org/10.3389/fchem.2020.580295
    5. Oleg A. Rakitin, Andrey V. Zibarev. Synthesis and Applications of 5‐Membered Chalcogen‐Nitrogen π‐Heterocycles with Three Heteroatoms. Asian Journal of Organic Chemistry 2018, 7 (12) , 2397-2416. https://doi.org/10.1002/ajoc.201800536
    6. Elena A. Chulanova, Nikolay A. Semenov, Nikolay A. Pushkarevsky, Nina P. Gritsan, Andrey V. Zibarev. Charge-transfer chemistry of chalcogen–nitrogen π-heterocycles. Mendeleev Communications 2018, 28 (5) , 453-460. https://doi.org/10.1016/j.mencom.2018.09.001
    7. Kathryn E. Preuss. Metal-radical coordination complexes of thiazyl and selenazyl ligands. Coordination Chemistry Reviews 2015, 289-290 , 49-61. https://doi.org/10.1016/j.ccr.2014.09.016
    8. Lidia S. Konstantinova, Ekaterina A. Knyazeva, Oleg A. Rakitin. Recent Developments in the Synthesis and Applications of 1,2,5-Thia- and Selenadiazoles. A Review. Organic Preparations and Procedures International 2014, 46 (6) , 475-544. https://doi.org/10.1080/00304948.2014.963454
    9. Anton Lonchakov, Oleg Rakitin, Nina Gritsan, Andrey Zibarev. Breathing Some New Life into an Old Topic: Chalcogen-Nitrogen π-Heterocycles as Electron Acceptors. Molecules 2013, 18 (8) , 9850-9900. https://doi.org/10.3390/molecules18089850
    10. R.T. Boeré, T.L. Roemmele. Chalcogen–Nitrogen Radicals. 2013, 375-411. https://doi.org/10.1016/B978-0-08-097774-4.00117-0
    11. René T. Boeré. Inorganic and organometallic radicals of main group elements. 2012, 22-57. https://doi.org/10.1039/9781849734837-00022
    12. Marc Fourmigué. Organic π‐Radicals in the Solid‐State: From Localised to Delocalised σ‐Bonding. 2012, 143-162. https://doi.org/10.1002/9781119945888.ch6
    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. https://doi.org/10.1007/s11172-011-0331-4

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    MENDELEY PAIRING EXPIRED
    Your Mendeley pairing has expired. Please reconnect