The Geometry of the Excited Charge Transfer States: Flattening or Twisting?

• Authors: J. Dobkowski , I. Sazanovich
• Languages of publication: EN

Abstracts

EN

Numerous molecules built of an electron acceptor and electron donor units linked together by single bond exhibit a peculiar behavior in their low-lying electronically excited states. N,N-diethylaminoacetophenone and 4-acetyl-4'-dimethylamino-biphenyl, having acetophenone as the acceptor and differentiated by the donors groups N(CH_3)_2 and dimethylaniline, respectively, were selected as the subject of study. To recognize the excited state relaxation paths the stationary and time-resolved spectroscopy in absorption and emission was applied. Experimental results indicate that after excitation in polar solvents N,N-diethylaminoacetophenone reduces to minimum the overlap between π-electron systems of the donor and acceptor groups relaxing to the twisted internal charge-transfer state; contrary to that, flattening of the 4-acetyl-4'-dimethylamino-biphenyl skeleton generates increase in the overlap of the π-electron systems.

Keywords

EN

33.50.-j; 61.66.Hq

Discipline

• 33.50.-j: Fluorescence and phosphorescence; radiationless transitions, quenching (intersystem crossing, internal conversion)(for energy transfer, see also section 34; for biophysical applications, see 87.64.kv)
• 61.66.Hq: Organic compounds

• Journal: Acta Physica Polonica A
• Year: 2007
• Volume: 112
• Issue: S
• Pages: S-127-S-142

Dates

published

2007-12

received

2007-10-26

Contributors

author

J. Dobkowski

• Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44, 01-224 Warsaw, Poland

author

I. Sazanovich

• Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44, 01-224 Warsaw, Poland

References

• 1. Z.R. Grabowski, J. Dobkowski, Pure Appl. Chem., 55, 245, 1983
• 2. Z.R. Grabowski, K. Rotkiewicz, W. Rettig, Chem. Rev., 105, 3899, 2003
• 3. J. Herbich, A. Kapturkiewicz, Chem. Phys., 170, 221, 1993
• 4. J. Herbich, A. Kapturkiewicz, Chem. Phys. Lett., 273, 8, 1997
• 5. J. Dobkowski, J. Waluk, Polish J. Chem., 4, 1389, 1993
• 6. O. Anner, Y. Haas, J. Phys. Chem., 90, 4298, 1986
• 7. S. Cogan, S. Zilberg, Y. Haas, J. Am. Chem. Soc., 128, 3335, 2006
• 8. K.A. Zachariasse, Chem. Phys. Lett., 320, 8, 2000
• 9. K.A. Zachariasse, M. Grobys, Th. Van der Haar, A. Hebecker, Yu.V. Ilíchev, O. Morawski, I. Rucker, W.J. Kuhnle, J. Photochem. Photobiol. A, 105, 373, 1997
• 10. Z.R. Grabowski, K. Rotkiewicz, A. Siemiarczuk, D.J. Cowley, W. Baumann, Nouv. J. Chim., 3, 443, 1979
• 11. C. Rulli`ere, Z.R. Grabowski, J. Dobkowski, Chem. Phys. Lett., 137, 408, 1987
• 12. P.B. Barbara, W. Jarzeba, in: Advances in Photochemistry, Vol. 15, Eds. D.H. Volman, G.S. Hammond, K. Gollnick, Wiley 1990, p. 1
• 13. M.J. Horng, J.A. Gardecki, A. Papazyan, M. Maroncelli, J. Phys. Chem., 99, 17331, 1995
• 14. S.I. Druzhinin, V. Galievsky, T. Yoshihara, K.A. Zachariasse, J. Phys. Chem. A, 110, 12760, 2006
• 15. J. Dobkowski, Z.R. Grabowski, J. Waluk, W. Kuhnle, W. Rettig, C. Rulli`ere, W. Yang, J. Adamus, J. Gebicki, Proc. Indian Acad. Sci. (Chem. Sci.), 104, 143, 1992
• 16. (a) G.M. Kosolapoff, J. Am. Chem. Soc., 69, 1651, 47. (b) R. Gawinecki, S. Andrzejak, A. Puchala, Org. Prep. Proced. Int., 30, 455, 1998
• 17. J. Jasny, J. Lumin., 17, 149, 1978
• 18. R.A. Velapoldi, in: National Bureau of Standards Special Publication 378, Accuracy in Spectrophotometry and Luminescence Measurements, Proc. Conf. NBS, Gaithersburg, MD, 1972, p. 231
• 19. J. Dobkowski, V.A. Galievsky, J. Jasny, I.V. Sazanovich, Polish J. Chem., 78, 961, 2004
• 20. T. Yoshihara, V.A. Galievsky, S.I. Druzhinin, S. Saha, K.A. Zachariasse, Photochem. Photobiol. Sci., 2, 342, 2003
• 21. W. Liptay, Z. Naturforsch. A, 17, 621, 1962
• 22. W. Liptay, in: Excited States, Vol. 1, Ed. E.C. Lim, Academic Press, New York 1974, p. 129
• 23. M. Maus, W. Rettig, D. Bonafoux, R. Lapouyade, J. Phys. Chem., 103, 3388, 1999
• 24. T. Shida, in: Electronic Absorption Spectra of Radical Ions. Physical Science Data, Vol. 34, Elsevier, Amsterdam 1988, p. 275
• 25. J. Dobkowski, E. Kirkor-Kamińska, J. Koput, A. Siemiarczuk, J. Lumin., 27, 339, 1982
• 26. S.K. Lower, M.A. El-Sayed, Chem. Rev., 66, 199, 1966
• 27. S. Dahne, W. Freyer, K. Teuchner, J. Dobkowski, Z.R. Grabowski, J. Lumin., 22, 37, 1980
• 28. J. Lipkowski, A. Tabaszewska, private information
• 29. M. Maus, W. Rettig, Chem. Phys., 218, 151, 1997
• 30. J. Herbich, J. Waluk, Chem. Phys., 188, 247, 1994
• 31. J. Dobkowski, W. Rettig, J. Waluk, Phys. Chem. Chem. Phys., 4, 4334, 2002
• 32. J. Dobkowski, J. Waluk, W. Yang, C. Rulli`ere, W. Rettig, New J. Chem., 21, 429, 1997
• 33. J.C.D. Brand, J. Mol. Spectrosc., 20, 359, 1966
• 34. C. Dubroca, Chem. Phys. Lett., 15, 207, 1972
• 35. C. Dubroca, P. Lozano, Chem. Phys. Lett., 24, 49, 1974

Identifiers

DOI

10.12693/APhysPolA.112.S-127