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    Electrostatic Regulation of TEMPO Oxidation by Distal Molecular Charges

    Access Status
    Open access
    Authors
    Zhang, L.
    Ciampi, Simone
    Gooding, J.J.
    Date
    2020
    Type
    Journal Article
    
    Metadata
    Show full item record
    Citation
    Zhang, L. and Ciampi, S. and Gooding, J.J. 2020. Electrostatic Regulation of TEMPO Oxidation by Distal Molecular Charges. ChemElectroChem. 7 (16): pp. 3522-3527.
    Source Title
    ChemElectroChem
    DOI
    10.1002/celc.202000817
    ISSN
    2196-0216
    Faculty
    Faculty of Science and Engineering
    School
    School of Molecular and Life Sciences (MLS)
    Funding and Sponsorship
    http://purl.org/au-research/grants/arc/CE140100036
    http://purl.org/au-research/grants/arc/FL150100060
    http://purl.org/au-research/grants/arc/DP190102659
    http://purl.org/au-research/grants/arc/FT190100148
    URI
    http://hdl.handle.net/20.500.11937/91722
    Collection
    • Curtin Research Publications
    Abstract

    We define, experimentally, the effect of intramolecular electric fields, generated from the positive charge of ferricenium cations, over the oxidation potential of 2,2,6,6-tetramethyl-1-piperdinyloxy (TEMPO). We synthesized a TEMPO derivative, where the nitroxide is linked to a ferrocene unit. We have used this molecule to study the influence on the electrostatic cross-talk between positively charged ferriceniums and TEMPO units by solvent dielectric, level of electrolytic support, and Lewis acid/base character of electrolyte ions. The magnitude of thermodynamic anodic shift of the TEMPO oxidation, after the ferrocene unit is converted to a ferricenium cation, increases with decreasing dielectric constant of the solvent, electrolytic concentration, and Lewis basicity strength (i. e. between ferriceniums and electrolyte anions). This work demonstrates an approach to use electrostatic forces, here delivered by intramolecular charged cations, to tune the oxidation energy for nitroxides in ionic solutions.

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