Journal of Solid State Electrochemistry

, Volume 19, Issue 1, pp 77–83 | Cite as

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

  • Bhushan Gadgil
  • Evgenia Dmitrieva
  • Pia Damlin
  • Timo Ääritalo
  • Carita Kvarnström
Original Paper


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.


Cyanopyridine Polyviologen derivative Reductive electropolymerization In situ ESR/UV-vis-NIR spectroelectrochemistry n-type materials 



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.

Supplementary material

10008_2014_2613_MOESM1_ESM.docx (113 kb)
ESM 1 (DOCX 113 kb)


  1. 1.
    Monk PMS (1998) The viologens: physicochemical properties, synthesis, and applications of the salts of 4,4′-bipyridine. WileyGoogle Scholar
  2. 2.
    Bird CL, Kuhn AT (1981) Electrochemistry of the viologens. Chem Soc Rev 10:49–82CrossRefGoogle Scholar
  3. 3.
    Chang H, Osawa M, Matsue T, Uchida I (1991) A novel polyviologen electrode fabricated by electrochemical crosslinking. J Chem Soc, Chem Commun:611–612Google Scholar
  4. 4.
    Hsu PF, Ciou WL, Chen PY (2008) Voltammetric study of polyviologen and the application of polyviologen-modified glassy carbon electrode in amperometric detection of vitamin C. J Appl Electrochem 38:1285–1292CrossRefGoogle Scholar
  5. 5.
    Kamata K, Kawai T, Iyoda T (2001) Anion-controlled redox process in a cross-linked polyviologen film toward electrochemical anion recognition. Langmuir 17:155–163CrossRefGoogle Scholar
  6. 6.
    Sen S, Saraidaridis J, Kim SY, Palmore GT (2013) Viologens as charge carriers in a polymer-based battery anode. ACS Appl Mater Interfaces 5:7825–7830CrossRefGoogle Scholar
  7. 7.
    Young Jo M, Eun Ha Y, Hyun Kim J (2012) Polyviologen derivatives as an interfacial layer in polymer solar cells. Solar Energy Mater Solar Cells 107:1–8CrossRefGoogle Scholar
  8. 8.
    Wang N, Damlin P, Esteban BM, Ääritalo T, Kankare J, Kvarnström C (2013) Electrochemical synthesis and characterization of copolyviologen films. Electrochim Acta 90:171–178CrossRefGoogle Scholar
  9. 9.
    Gadgil B, Damlin P, Ääritalo T, Kankare J, Kvarnström C (2013) Electrosynthesis and characterization of viologen cross-linked thiophene copolymer. Electrochim Acta 97:378–385CrossRefGoogle Scholar
  10. 10.
    Gadgil B, Damlin P, Ääritalo T, Kvarnström C (2014) Electrosynthesis of viologen cross-linked polythiophene in ionic liquid and its electrochromic properties. Electrochim Acta 133:268–274CrossRefGoogle Scholar
  11. 11.
    Akahoshi H, Toshima S, Itaya K (1981) Electrochemical and spectroelectrochemical properties of polyviologen complex modified electrodes. J Phys Chem 85:818–822CrossRefGoogle Scholar
  12. 12.
    Dunsch L (2011) Recent advances in in situ multi-spectroelectrochemistry. J Solid State Electrochem 15:1631–1646Google Scholar
  13. 13.
    Sydam R, Deepa M, Joshi AG (2013) A novel 1,1′-bis[4-(5,6-dimethyl-1H-benzimidazole-1-yl)butyl]-4,4′-bipyridinium dibromide (viologen) for a high contrast electrochromic device. Org Electron 14:1027–1036CrossRefGoogle Scholar
  14. 14.
    Sano N, Tomita W, Hara S, Min C, Lee J, Oyaizu K, Nishide H (2013) Polyviologen hydrogel with high-rate capability for anodes toward an aqueous electrolyte-type and organic-based rechargeable device. ACS Appl Mater Interfaces 5:1355–1361CrossRefGoogle Scholar
  15. 15.
    Meana-Esteban B, Petr A, Kvarnström C, Ivaska A, Dunsch L (2014) Poly(2-methoxynaphthalene): a spectroelectrochemical study on a fused ring conducting polymer. Electrochim Acta 115:10–15CrossRefGoogle Scholar
  16. 16.
    Österholm A, Petr A, Kvarnström C, Ivaska A, Dunsch L (2008) The nature of the charge carriers in polyazulene as studied by in situ electron spin resonance-UV-visible-near-infrared spectroscopy. J Phys Chem B 112:14149–14157CrossRefGoogle Scholar
  17. 17.
    Lee C, Lee YM, Moon MS, Park SH, Park JW, Kim KG, Jeon S (1996) UV-vis-NIR and Raman spectroelectrochemical studies on viologen cation radicals: evidence for the presence of various types of aggregate species. J Electroanal Chem 416:139–144CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2014

Authors and Affiliations

  1. 1.Turku University Centre for Materials and Surfaces (MATSURF), Laboratory of Materials Chemistry and Chemical AnalysisUniversity of TurkuTurkuFinland
  2. 2.University of Turku Graduate School (UTUGS)TurkuFinland
  3. 3.Center of SpectroelectrochemistryIFW DresdenDresdenGermany

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