Abstract
The results of study on the properties of dimers of thiamonomethine-and thiatrimethinecyanines (thiacarbocyanines) in the ground and electronically excited states in aqueous solutions are presented. Dimers of cyanine dyes have the sandwiched structure with near-parallel alignment of the polymethine chains of the monomers in the dimer. The formation of dimers is manifested by two absorption bands of different intensities due to splitting of the S* level of the monomers upon their resonance interaction. Dimers of thiacarbocyanines are characterized by a low fluorescence quantum yield φfl as compared to monomers; however, φfl of dimers of thiamonomethinecyanines are markedly higher than that of monomers. Dimers of cyanine dyes are also characterized by a relatively high quantum yield of intersystem crossing to the triplet state. In the triplet-triplet absorption spectra, two bands of different intensities are revealed, which are due to the splitting of the higher triplet level of the monomers that form the dimer. In the presence of electron donors (ascorbic acid, hydroquinone) and/or acceptors (p-benzoquinone, p-nitroacetophenone, methylviologen), the triplet state of dimers is quenched as a result of electron transfer yielding radical products. Dimers in the triplet state can serve as photosensitizers of redox reactions.
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References
The Theory of the Photographic Process, James, T.H., Ed., New York: Macmillan, 1977.
Mal’tsev, E.I., Lypenko, D.A., Shapiro, B.I., and Vannikov, A.V., Zh. Nauchn. Prikl. Fotogr., 2001, vol. 46, no. 1, p. 13.
Scheblykin, I.G., Lepnev, L.S., Vitukhnovsky, A.G., and Van der Auweraer, M., J. Lumin., 2001, vol. 94–95, p. 461.
Bourbon, S., Gao, M.Y., and Kirstein, S., Synth. Met., 1999, vol. 101, p. 152.
Sasaki, F. and Kobayashi, S., J. Lumin., 1997, vol. 72–74, p. 538.
Markov, R.V., Plekhanov, A.I., Rautian, S.G., Safonov, V.P., Orlova, N.A., Shelkovnikov, V.V., and Volkov, V.V., Opt. Spektrosk., 1998, vol. 85, no. 4, p. 643.
Khimenko, V., Chibisov, A.K., and Görner, H., J. Phys. Chem. A, 1997, vol. 101, p. 7304.
Avdeeva, V.I. and Shapiro, B.I., Zh. Nauchn. Prikl. Fotogr., 2000, vol. 45, no. 6, p. 27.
Görner, H. and Chibisov, A.K., CRC Handbook of Organic Photochemistry and Photobiology, London: CRC, 2004.
Kuz’min, V.A., Usp. Nauchn. Fotogr., 1984, vol. 22, p. 90.
Tyutyulkov, N., Fabian, J., Mehlhorn, A., Dietz, F., and Tadjer, A., Polymethine Dyes. Structure and Properties, Sofia: St. Kliment Ohridski Univ., 1991.
Korobov, V.E. and Chibisov, A.K., Usp. Khim., 1983, vol. 52, p. 43.
Chibisov, A.K., Shvedov, S.V., and Görner, H., J. Photochem. Photobiol., A, 2001, vol. 141, no. 1, p. 39.
Chibisov, A.K., J. Photochem., 1976/1977, vol. 6, p. 199.
Chibisov, A.K., Zakharova, G.V., and Görner, H., Phys. Chem. Chem. Phys., 2001, vol. 3, p. 44.
Chibisov, A.K., Zakharova, G.V., and Görner, H., Phys. Chem. Chem. Phys., 1999, vol. 1, p. 1455.
Zakharova, G.V. and Chibisov, A.K., Khim. Vys. Energ., 2001, vol. 35, no. 6, p. 454 [High Energy Chem., 2001, vol. 35, no. 6, p. 417].
Chibisov, A.K., Zakharova, G.V., and Shapiro, B.I., J. Inf. Recording, 1996, vol. 22, p. 313.
Atabekyan, L.S. and Chibisov, A.K., Khim. Vys. Energ., 2007, vol. 41, no. 2 [High Energy Chem., 2007, vol. 41, no. 2, p.
Ishchenko, A.A., Stroenie i spektral’no-lyuminestsentnye svoistva polimetinovykh krasitelei (Structure and Spectral-Luminescence Properties of Polymethine Dyes), Kiev: Naukova Dumka, 1994.
Chibisov, A.K., Slavnova, T.D., and Görner, H., Chem. Phys., 2004, vol. 299, p. 1.
Zakharova, G.V. and Chibisov, A.K., Khim. Vys. Energ., 1998, vol. 32, no. 6, p. 446 [High Energy Chem., 1998, vol. 32, no. 6, p. 403].
Kasha, M., Rawls, H.R., and El-Bayoumi, M.A., Molecular Spectroscopy, London: Butterworths, 1965.
McRae, E.G. and Kasha, M., Physical Processes in Radiation Biology, London: Academic, 1964.
Matsubara, T. and Tanaka, T., J. Imaging Sci., 1991, vol. 35, p. 274.
Zhang, Z., Hao, J., Wu, B., and Yuan, H., J. Imaging Sci., 1995, vol. 39, p. 373.
Valdes-Aguilera, O. and Neckers, D.C., Acc. Chem. Res., 1989, vol. 22, p. 171.
Herz, A.H., Photogr. Sci. Eng., 1974, vol. 18, p. 323.
Chibisov, A.K., Prokhorenko, V.I., and Görner, H., Chem. Phys., 1999, vol. 250, p. 47.
Zakharova, G.V., Makedonskaya, D.A., and Chibisov, A.K., Zh. Nauchn. Prikl. Fotogr., 2001, vol. 46, no. 6, p. 10.
Slavnova, T.D., Chibisov, A.K., and Görner, H., J. Phys. Chem. A, 2002, vol. 106, p. 10985.
Chibisov, A.K., Zakharova, G.V., Görner, H., Sogulyaev, Yu.A., Mushkalo, I.L., and Tolmachev, A.I., J. Phys. Chem., 1995, vol. 99, no. 3, p. 886.
Whillians, D.W., Radiat. Phys. Chem., 1977, vol. 10, p. 335.
Chibisov, A.K., Slavnova, T.D., and Görner, H., Chem. Phys. Lett., 2004, vol. 386, p. 301.
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Original Russian Text © A.K. Chibisov, 2007, published in Khimiya Vysokikh Energii, 2007, Vol. 41, No. 3, pp. 239–248.
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Chibisov, A.K. Photonics of dimers of cyanine dyes. High Energy Chem 41, 200–209 (2007). https://doi.org/10.1134/S0018143907030071
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DOI: https://doi.org/10.1134/S0018143907030071