Abstract
Symmetric N,N′-disubstituted salts of 4,4′-bipyridyl (viologens) are synthesized and described. It is shown by cyclic voltammetry that disubstituted salts of 4,4′-bipyridyl have a tendency toward reversible two-electron reduction. Normal first and second step oxidation-reduction potentials with respect to saturated silver chloride electrodes at various potential scan rates are found. The spectra of the high-resolution electron paramagnetic resonance of viologen cation radicals formed during the reduction of N,N′-disubstituted salts of 4,4′-bipyridyl are obtained and interpreted. It is established that the nature of substitutes and counterions in a viologen molecule considerably influences the distribution of its spin density, voltammetric curves, and electro-optical properties.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
P. M. S. Monk, R. J. Mortimer, and D. R. Rosseinsky, Electrochromism: Fundamentals and Applications (Cambridge Univ. Press, 2007).
P. M. S. Monk, The Viologens (Wiley, New York, 1998).
V. F. Vargalyuk, T. I. Starokozheva, and Yu. M. Loshkarev, Sov. Electrochem. 15, 1337 (1979).
A. G. Evans, J. C. Evans, and M. W. Baker, J. Am. Chem. Soc. 99, 5582 (1977).
J. C. Evans, C. R. Morris, D. W. Clark, et al., J. Chem. Soc., Perkin Trans. 2, p. 1541 (1988).
W. Kremers and J. W. Steel, Can. J. Chem. 45, 745 (1967).
K. A. Bilevich and O. Yu. Okhlobystin, Russ. Chem. Rev. 37, 954 (1968).
M. Beizer and H. Lund, Organic Electrochemistry (Marcel Dekker, New York, 1983; Khimiya, Moscow, 1988), p. 470.
A. A. Granovsky, Firefly, Vers. 7.1. http://classic.chem.msu.su/gran/firefly/index.html.
M. W. Schmidt, K. K. Baldridge, J. A. Boatz, et al., J. Comput. Chem. 14, 1347 (1993).
L. A. Kundryutskova and N. N. Lonina, Uchen. Zap. MITKhT 13, 49 (2005).
B. I. Shapiro, V. V. Minin, and Ya. K. Syrkin, Zh. Strukt. Khim. 14, 642 (1973).
H. S. Gutowsky and C. S. Johnson, J. Chem. Phys. 39, 58 (1963).
E. A. Polenov, Izv. Akad. Nauk, Ser. Fiz. 68, 1066 (2004).
Author information
Authors and Affiliations
Corresponding author
Additional information
Original Russian Text © M.I. Zakirov, N.N. Efimov, P.V. Mel’nikov, E.L. Nodova, V.V. Minin, 2013, published in Zhurnal Fizicheskoi Khimii, 2013, Vol. 87, No. 8, pp. 1398–1404.
Rights and permissions
About this article
Cite this article
Zakirov, M.I., Efimov, N.N., Mel’nikov, P.V. et al. Electronic structure and electro-optical properties of ion radicals formed during the reduction of N,N′-dialkylsubstituted salts of 4,4′-bipyridyl. Russ. J. Phys. Chem. 87, 1386–1392 (2013). https://doi.org/10.1134/S0036024413070364
Received:
Published:
Issue Date:
DOI: https://doi.org/10.1134/S0036024413070364