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Redox reactions in a linear polyviologen derivative studied by in situ ESR/UV-vis-NIR spectroelectrochemistry

Journal of Solid State Electrochemistry volume 19, pages 77–83 (2015)Cite this article

Abstract

It is well-known that reductive electropolymerization of cyanopyridinium moieties yields to viologenic materials. In this work, a monomer with two electropolymerizable cyanopyridinium groups separated by a six carbon spacer (CNP) has been synthesized. Its electropolymerization in aqueous electrolyte results in a linear polyviologen (PV) derivative, a purple-colored film deposited on the electrode surface. Cyclic voltammetry (CV) of PV films displays two well-resolved one-electron redox processes at c.a. −0.5 and −1.0 V vs. Ag/AgCl. Fourier transform infrared (FTIR) spectral analysis shows successful polymerization of PV from the CNP monomer. In situ electron spin resonance (ESR)/UV-vis-NIR spectroelectrochemistry was used in order to simultaneously determine the polycation radical as well as the magnetic and optical response of the redox PV system. The single-line ESR spectrum observed at the first reduction peak of PV film was assigned to the formation of stable viologen cation radical species within the polymer matrix, exhibiting the characteristic UV-vis-NIR viologen cation radical absorption bands. The electrosynthesized linear PV system represents a promising stable redox active n-type material for organic rechargeable devices.

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Acknowledgments

We gratefully acknowledge the financial support from Academy of Finland. BG would like to thank the Center of Spectroelectrochemistry, IFW Dresden for providing research facilities. BG also would like to thank Frank Ziegs for the technical support and fruitful discussions.

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Authors and Affiliations

  1. Turku University Centre for Materials and Surfaces (MATSURF), Laboratory of Materials Chemistry and Chemical Analysis, University of Turku, 20014, Turku, Finland

    Bhushan Gadgil, Pia Damlin, Timo Ääritalo & Carita Kvarnström

  2. University of Turku Graduate School (UTUGS), 20014, Turku, Finland

    Bhushan Gadgil

  3. Center of Spectroelectrochemistry, IFW Dresden, Helmholtzstrasse 20, 01069, Dresden, Germany

    Evgenia Dmitrieva

Authors
  1. Bhushan Gadgil
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  2. Evgenia Dmitrieva
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  3. Pia Damlin
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  4. Timo Ääritalo
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  5. Carita Kvarnström
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Correspondence to Bhushan Gadgil or Carita Kvarnström.

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Gadgil, B., Dmitrieva, E., Damlin, P. et al. Redox reactions in a linear polyviologen derivative studied by in situ ESR/UV-vis-NIR spectroelectrochemistry. J Solid State Electrochem 19, 77–83 (2015). https://doi.org/10.1007/s10008-014-2613-x

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