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Redox behaviour of some asymmetrically substituted viologens and an alkyl bridged bis-viologen in non-aqueous solvents: a voltammetric and spectroscopic investigation

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Abstract

A compound library of seven asymmetrically substituted viologens and, additionally, a bis-viologen is investigated by voltammetric and EPR- and UV–Vis spectroelectrochemical techniques as well as diffusion-ordered nuclear magnetic resonance (NMR) spectroscopy. In acetonitrile-based electrolytes, all compounds show a stepwise two electron chemically and electrochemically reversible reduction of the viologen moieties. In the case of the bis-viologen, peak potential difference data indicate a weak difference in the formal potentials of the two non-conjugated redox systems. Diffusion coefficients from cyclic voltammetric and pulse gradient spin echo NMR experiments are comparable for all mono-viologens while the size and saturation of the side chain in the mono-viologen compounds has only a minor influence on this transport property. The semi-quinone forms of the viologens are highly stable with respect to disproportionation and they are EPR active. For the mono-viologens, coupling constants for all hydrogen and nitrogen nuclei interacting with the unpaired electron were determined. The bis-viologen forms a bis(radical cation) as well as an EPR-silent (but UV-detectable) π-dimer. Furthermore, the effect of weakly coordinating anions on the different redox states is reported.

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Acknowledgments

The authors thank J. Edrich and P. Finkbeiner for preliminary experiments. The authors also thank the Deutsche Metrohm GmbH & Co. KG Filderstadt, Germany, for providing the UV–Vis spectroelectrochemical setup. AR thanks the Universität Tübingen for an LGFG fellowship.

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Author notes

  1. Adrian Ruff

    Present address: Institut für Polymerchemie, Universität Stuttgart, Pfaffenwaldring 55, 70569, Stuttgart, Germany

Authors and Affiliations

  1. Institut für Organische Chemie, Auf der Morgenstelle 18, 72076, Tübingen, Germany

    Monika Passon, Adrian Ruff, Paul Schuler & Bernd Speiser

  2. Institut für Anorganische Chemie, Auf der Morgenstelle 18, 72076, Tübingen, Germany

    Wolfgang Leis

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  1. Monika Passon
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Correspondence to Bernd Speiser.

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Dedicated to the late Lothar Dunsch, a colleague and friend.

Two-electron-transfer redox systems. Part 9. for Part 8, see ref. [1]; the list of authors is ordered alphabetically within the participating institutes.

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Passon, M., Ruff, A., Schuler, P. et al. Redox behaviour of some asymmetrically substituted viologens and an alkyl bridged bis-viologen in non-aqueous solvents: a voltammetric and spectroscopic investigation. J Solid State Electrochem 19, 85–101 (2015). https://doi.org/10.1007/s10008-014-2629-2

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  • DOI: https://doi.org/10.1007/s10008-014-2629-2

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