Journal of Chemical Sciences

, Volume 120, Issue 1, pp 45–55 | Cite as

Relaxation dynamics in the excited states of a ketocyanine dye probed by femtosecond transient absorption spectroscopy

  • Jahur A. Mondal
  • Sandeep Verma
  • Hirendra N. Ghosh
  • Dipak K. Palit
Article
First Online:

Abstract

Relaxation dynamics of the excited singlet states of 2,5-bis-(N-methyl-N-1,3-propdienylaniline)-cyclopentanone (MPAC), a ketocyanine dye, have been investigated using steady-state absorption and emission as well as femtosecond time-resolved absorption spectroscopic techniques. Following photoexcitation using 400 nm light, the molecule is excited to the S2 state, which is fluorescent in rigid matrices at 77 K. S2 state is nearly non-fluorescent in solution and has a very short lifetime (0.5 ± 0.2 ps). In polar aprotic solvents, the S1 state follows a complex multi-exponential relaxation dynamics consisting of torsional motion of the donor groups, solvent re-organization as well as photoisomerization processes. However, in alcoholic solvents, solvent re-organization via intermolecular hydrogen-bonding interaction is the only relaxation process observed in the S1 state. In trifluoroethanol, a strong hydrogen bonding solvent, conversion of the non-hydrogen-bonded form, which is formed following photoexcitation, to the hydrogen-bonded complex has been clearly evident in the relaxation process of the S1 state.

Keywords

Ketocyanine dye excited state dynamics S2-fluoroscence photoisomerization solvent re-organization 
This is a preview of subscription content, log in to check access.

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    Kessler M A and Wolfbeis O S 1991 Spectrochim. Acta. A47 187Google Scholar
  2. 2. (a)
    Banerjee D, Laha A K and Bagchi S 1995 Indian J. Chem. A34A 94Google Scholar
  3. 2. (b)
    Banerjee D, Laha A K and Bagchi S 1995 J. Photochem. Photobiol. A: Chem. 85 153CrossRefGoogle Scholar
  4. 2. (c)
    Banerjee D, Mondal S, Ghosh, S and Bagchi S 1995 J. Photochem. Photobiol. A: Chem. 90 171CrossRefGoogle Scholar
  5. 2. (d)
    Banerjee D, Das P K, Mondal S, Ghosh S and Bagchi S 1996 J. Photochem. Photobiol. A: Chem. 98 183CrossRefGoogle Scholar
  6. 2. (e)
    Banerjee D and Bagchi S 1996 J. Photochem. Photobiol. A: Chem. 101 57CrossRefGoogle Scholar
  7. 2. (f)
    Pramanik R, Das P K and Bagchi S 1999 J. Photochem. Photobiol. A: Chem. 124 135CrossRefGoogle Scholar
  8. 2. (g)
    Pramanik R, Das P K and Bagchi S 2000 Phys. Chem. Chem. Phys. 2 4307CrossRefGoogle Scholar
  9. 2. (h)
    Pramanik R, Das P K, Banerjee D and Bagchi S 2001 Chem. Phys. Lett. 341 507CrossRefGoogle Scholar
  10. 2. (i)
    Shannigrahi M, Pramanik R and Bagchi S 2003 Spectrochim. Acta A59 2921Google Scholar
  11. 2. (j)
    Das P K Pramanik R, Banerjee D and Bagchi S 2000 Spectrochim. Acta A56 2763Google Scholar
  12. 3.
    Marcotte N and Fery-Forgues S 2000 J. Photochem. Photobiol. A: Chem. 130 133CrossRefGoogle Scholar
  13. 4.
    Doroshenko A O and Pivovarenko V G 2003 J. Photochem. Photobiol. A. Chem. 156 55CrossRefGoogle Scholar
  14. 5.
    Doroshenko A O, Bilokin M D and Pivovarenko V G 2004 J. Photochem. Photobiol. A: Chem. 163 95CrossRefGoogle Scholar
  15. 6.
    Pivovarenko V G, Klueva A V, Doroshenko A O and Demchenko A P 2000 Chem. Phys. Lett. 325 389CrossRefGoogle Scholar
  16. 7.(a)
    Lobnik A and Wolfbeis O S 1998 Analyst 123 2247CrossRefGoogle Scholar
  17. 7.(b)
    Reichardt C 1994 Chem. Rev. 94 2319CrossRefGoogle Scholar
  18. 8.
    Doroshenko A O, Grigorovich A V, Posokhov E A, Pivovarenko A G and Demchenko A P 1999 J. Mol. Eng. 8 199CrossRefGoogle Scholar
  19. 9.
    Doroshenko A O, Sychevskaya L B, Grygorovych, A V and Pivovarenko V G 2002 J. Fluoresc. 12 451CrossRefGoogle Scholar
  20. 10.
    Rurack K, Dekhtyar M L, Bricks J L, Resch-Genger U and Rettig W 1999 J. Phys. Chem. A103 9626Google Scholar
  21. 11.
    Barnabas M V, Liu A, Trifanac A D, Krougauz V V and Chang C T 1992 96 212Google Scholar
  22. 12.
    Chambers W J and Eaton D F 1986 J. Imaging Sci. 13 230Google Scholar
  23. 13.
    Baun M D and Henry C P 1972 Ger. Offen. 2 133; 315; Baun M D and Henry C P 1970 US Appl. 53 686Google Scholar
  24. 14.
    Marcotte N, Ferry-Fogues S, Lavabre D, Marquet S and Pivovarenko V G 1999 J. Phys. Chem. 103 3163Google Scholar
  25. 15. (a)
    Fabian J, Nakazami H and Matsuoka M 1992 Chem. Rev. 92 1197CrossRefGoogle Scholar
  26. 15. (b)
    Mishra A, Behera R K, Behera P K, Mishra B K and Behera G B 2000 Chem. Rev. 100 1973CrossRefGoogle Scholar
  27. 16. (a)
    Frank H A 2001 Arch. Biochem. Biophys. 385 53CrossRefGoogle Scholar
  28. 16. (b)
    Poliska T and Sundstorm V 2004 Chem. Rev. 104 2021CrossRefGoogle Scholar
  29. 16. (c)
    Koyama Y, Kuki M, Anderson P O and Gilbro T 1996 Photochem. Photobiol. 63 243CrossRefGoogle Scholar
  30. 17. (a)
    Lu D, Chen G, Perry J W and Beddard III W A 1994 J. Am. Chem. Soc. 116 10679CrossRefGoogle Scholar
  31. 17. (b)
    Alain V, Thouin L, Bkanchard-Desce M, Gubler U, Bosshard C, Gunter P, Muller J, Fort A and Barzoukas M 1999 Adv. Mater. 11 1210CrossRefGoogle Scholar
  32. 17. (c)
    Alain V, Blanchard-Dessce M, Ladous-Rak I and Zyss J 2000 Chem. Commun 353Google Scholar
  33. 18.
    Mondal J A, Ghosh H N, Mukherjee T, Palit D K 2005 J. Phys. Chem. A109 6836Google Scholar
  34. 19.
    Mondal J A, Ghosh H N, Ghanty T K, Mukherjee T and Palit D K 2006 J. Phys. Chem. A110 3432Google Scholar
  35. 20.
    El-Sayed M A 1963 J. Phys. Chem. 38 2834CrossRefGoogle Scholar
  36. 21.
    Kovalenko S A, Ernsting N P and Ruthmann J 1997 J. Chem. Phys. 106 3504CrossRefGoogle Scholar
  37. 22.
    Simon J D 1988 Acc. Chem. Res. 21 128CrossRefGoogle Scholar
  38. 23.
    Davies M 1969 Dielectric properties and molecular behaviour (eds) N F Hill, W E Vaughan, A H Price and M Davies (London: Van Nostrand)Google Scholar
  39. 24.
    Lin Y and Jonah C D 1993 J. Phys. Chem. 97 295CrossRefGoogle Scholar
  40. 25.
    Horng H L, Dahl K, Jones II G and Maroncelli M 1999 Chem. Phys. Lett. 315 363CrossRefGoogle Scholar
  41. 26.
    Ludwig R and Zeidler M D 1966 Mol. Phys. 10 451CrossRefGoogle Scholar
  42. 27.
    Akemabn W, Laage D, Plaza P, Martin M M and Blanchard-Dessce M 2007 J. Phys. Chem. B106 (in press)Google Scholar
  43. 28.
    Hynes J T 1985 Theory of chemical reaction dynamics (ed.) M Bear (CRC: Boca Raton) vol IVGoogle Scholar
  44. 29.
    Hynes J T 1985 Annu. Rev. Phys. Chem. 36 573CrossRefGoogle Scholar
  45. 30.
    Berne B J, Borkovec M and Straub J E 2001 J. Phys. Chem. A105 6294Google Scholar
  46. 31.
    Kramers H 1940 Physica 7 284CrossRefGoogle Scholar
  47. 32. (a)
    Yu J and Berg M 1993 Chem. Phys. Lett. 208 315CrossRefGoogle Scholar
  48. 32. (b)
    Benigno A J, Ahmed E and Berg M 1996 J. Chem. Phys. 104 7382CrossRefGoogle Scholar
  49. 33.
    Garg S K and Smyth C P 1965 J. Phys. Chem. 69 1294CrossRefGoogle Scholar
  50. 34.
    Bertolini D, Cassettari M and Salvetti G 1982 J. Chem. Phys. 76 325CrossRefGoogle Scholar
  51. 35.
    Matsumoto M and Gubbins K 1990 J. Chem. Phys. 93 1981CrossRefGoogle Scholar
  52. 36. (a)
    Maroncelli M, MacInnis J and Fleming G. R. 1989 Science 243 1674CrossRefGoogle Scholar
  53. 36. (b)
    Maroncelli M 1993 J. Mol. Liq. 57 1CrossRefGoogle Scholar
  54. 36. (c)
    Maroncelli M, Castner Jr E W, Bagchi B and Fleming G R 1988 Faraday Discuss. Chem. Soc. 85 199CrossRefGoogle Scholar
  55. 36. (d)
    Horng M L, Gardecki J A, Papazyan A and Maroncelli M 1995 J. Phys. Chem. 99 17311CrossRefGoogle Scholar
  56. 37.
    Kenney-Wallace G A, Paone S and Kalpouzos C 1988 Faraday Discuss. Chem. Soc. 85 185CrossRefGoogle Scholar
  57. 38.
    Biswas R, Nandi N and Bagchi B 1997 J. Phys. Chem. B101 2968Google Scholar
  58. 39. (a)
    Gale G M, Gallot G, Hache F, Lascoux N, Bratos S and Leicknam J-C 1999 Phys. Rev. Lett. 82 1086Google Scholar
  59. 39. (b)
    Woutersen S and Bakker H J 1999 Phys. Rev. lett. 83 2707CrossRefGoogle Scholar
  60. 40.
    Lock A J, Woutersen S and Bakker H J 2001 J. Phys. Chem. A105 1238Google Scholar
  61. 41.
    Joo T, Jia Y, Yu J-Y, Lang M J and Fleming G R 1996 J. Chem. Phys. 104 6089CrossRefGoogle Scholar

Copyright information

© Indian Academy of Sciences 2008

Authors and Affiliations

  • Jahur A. Mondal
    • 1
  • Sandeep Verma
    • 1
  • Hirendra N. Ghosh
    • 1
  • Dipak K. Palit
    • 1
  1. 1.Radiation and Photochemistry DivisionBhabha Atomic Research CentreMumbaiIndia

Personalised recommendations