Journal of Solid State Electrochemistry

, Volume 5, Issue 1, pp 17–22 | Cite as

Voltammetry of electroactive liquid redox systems: anion insertion and chemical reactions in microdroplets of para-tetrakis(6-methoxyhexyl) phenylenediamine, para- and meta-tetrahexylphenylenediamine

  • Frank Marken
  • Alastair N. Blythe
  • Jay D. Wadhawan
  • Richard G. Compton
  • Steven D. Bull
  • Robin T. Aplin
  • Stephen G. Davies
ORIGINAL PAPER

Abstract

The effect of the structure of the organic precursor molecule on the electroinsertion of anions and on the formation of materials in the ionic liquid state is compared for three compounds, para-N, N, N′, N′-tetrahexylphenylenediamine (p-THPD), meta-N, N, N′, N′-tetrahexylphenylene diamine (m-THPD), and para-N, N, N′, N′-tetrakis(6-methoxyhexyl)phenylenediamine (p-TMHPD), by characterising their condensed phase voltammetric properties in aqueous media. The electrochemically driven anion insertion in p-THPD and p-TMHPD in the presence of ClO4, F, Cl, Br, I, and SO42− is shown to be extremely sensitive to structure. The introduction of the methoxy end groups in p-TMHPD causes (1) a considerable shift to more negative electroinsertion potentials, (2) a less stable response which upon continuous cycling decreases, and (3) considerably lower anion selectivity. For the insertion of sulfate, only p-TMHPD yields an electrochemical response which is shown to be consistent with insertion of the dianion SO42−. The electrochemical oxidation of a deposit of m-THPD is accompanied by anion insertion and a chemical reaction step in an EC-type electrochemical process. The product of the chemical step is electrochemically active and results in a new reversible electroinsertion process. Starting materials and products of the microdroplet reactions are characterised by Maldi-TOF mass spectrometry and a reaction mechanism based on condensed phase polymerisation is proposed.

Key words Ionic liquid Microdroplet Modified electrodes Electroinsertion 

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Copyright information

© Springer-Verlag Berlin Heidelberg 2001

Authors and Affiliations

  • Frank Marken
    • 1
  • Alastair N. Blythe
    • 1
  • Jay D. Wadhawan
    • 1
  • Richard G. Compton
    • 1
  • Steven D. Bull
    • 2
  • Robin T. Aplin
    • 2
  • Stephen G. Davies
    • 2
  1. 1.Physical & Theoretical Chemistry Laboratory, Oxford University, South Parks Road, Oxford OX1 3QZ, UK e mail: Frank@physchem.ox.ac.uk Tel.: +44-1865-275448; Fax: +44-1865-275410GB
  2. 2.Dyson Perrins Laboratory, Oxford University, South Parks Road, Oxford OX1 3QY, UKGB

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