Abstract
Methylviologen (MV2+) forms ion-pair electron donor-acceptor complexes in aqueous solution with C2O4 2− and EDTA. From the results of pulsed laser excitation at 355 nm, a model is proposed in which the ion-pair complexes of MV2+ exist as “pseudo-micelle” aggregates; absorption of light generates MV+· and an oxidized-donor radical within the aggregate. The irreversible conversion of the oxidized radical to a reducing radical, in competition with geminate pair back electron-transfer, leads to the formation of a second equivalent of MV+· within the aggregate structure; the MV+· species are ultimately released into bulk solution as the aggregate structure equilibrates. The values of Ф(MV+·) from continuous photolysis are a measure of the dependence of the rate of geminate pair back electron-transfer on the structure of the aggregate, state of protonation of the species, and the states populated in the light-absorption process.
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References
M.Z. Hoffman, D.R. Prasad, G. Jones, II, and V. Malba, J. Am. Chem. Soc., 105, 6360 (1983).
J.P. Kuczynski, B.H. Milosavijevic, A.G. Lappin, and J.K. Thomas, Chem. Phys. Lett., 104, 149 (1984).
J.R. Barnett, A.S. Hopkins, and A. Ledwith, J. Chem. Soc., Perkin Trans. 2, 80 (1973).
Organic Charge-Transfer Complexes, R. Foster, ed., Academic Press, London, 1969.
H.A. Benesi and J.H. Hildebrand, J. Am. Chem. Soc., 71, 2703 (1949).
D.R. Prasad and M.Z. Hoffman, J. Phys. Chem., 88, 5660 (1984).
Critical Stability Constants, A.E. Martell and R.M. Smith, eds., Plenum Press, New York, 1974, Vol. 1, p. 204.
D.R. Prasad, M.Z. Hoffman, Q.G. Mulazzani, and M.A.J. Rodgers, J. Am. Chem. Soc., 108, 5135 (1986).
D.R. Prasad and M.Z. Hoffman, J. Chem. Soc., Faraday Trans. 2, 82, 2275 (1986).
M. Zisk and G. Jones, II, J. Org. Chem., 51, 947 (1986).
R.S. Mulliken, J. Am. Chem. Soc., 74, 811 (1952).
Q.G. Mulazzani, M. D’Angelantonio, M. Venturi, M.Z. Hoffman, and M.A.J. Rodgers, J. Phys. Chem., 90, 5347 (1986).
Q.G. Mulazzani, M. Venturi, and M.Z. Hoffman, J. Phys. Chem., 89, 722 (1985).
L.A. Summers, The Bipyridinium Herbicides, Academic Press, London, 1980, Chap. 4.
E.M. Kosower and J.L. Cotter, J. Am. Chem. Soc., 86, 5524 (1964).
T.W. Ebbesen and M. Ohgushi, Photochem. Photobiol., 38, 251 (1983).
J.H. Fendler, J. Phys. Chem., 89, 2730 (1985).
T. Watanabe and K. Honda, J. Phys. Chem., 86, 2617 (1982).
J.G. Clavert and J.N. Pitts, Jr., Photochemistry, Wiley, New York, 1966, p. 784.
A.W.H. Mau, J.M. Overbeek, J.W. Loder, and W.H.F. Sasse, J. Chem. Soc., Faraday Trans. 2, 82, 869 (1986).
N.J. Turro, Modern Molecular Photochemistry, Benjamin/Cummings, Menlo Park, CA, 1978.
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© 1987 D. Reidel Publishing Company
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Hoffman, M.Z., Prasad, D.R. (1987). Photoinduced Charge Separation in Ion-Pair Electron Donor-Acceptor Aggregates. In: Balzani, V. (eds) Supramolecular Photochemistry. NATO ASI Series, vol 214. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-3979-0_10
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DOI: https://doi.org/10.1007/978-94-009-3979-0_10
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