Skip to main content
SpringerLink
Log in

Pressure dependence of the dual luminescence of twisting molecules. The case of substituted 2,3-naphthalimides

  • Full Paper
  • Published:
Photochemical & Photobiological Sciences Aims and scope Submit manuscript

Abstract

The effect of high pressure (up to 5 kbar) has been studied for triacetin solutions of 2-phenyl-2,3-dihydro-1H-benzo[f]isoindole-1,3dione 1 (N-phenyl-2,3-naphthalimide) and its 3-fluorophenyl- (2), 4-carbethoxyphenyl- (4) and 4-methoxyphenyl- (5) derivatives which all show dual fluorescence. When the N-phenyl group is unsubstituted (compound 1) or substituted with electron-attracting groups (2 and 4), the increase of pressure over the solution decreases slightly the emission at the long-wavelengths (LW) and increases dramatically the intensity of the short-wavelength (SW) fluorescence. Plotting the logarithm of the SW/LW fluorescence quantum yield ratio for compounds 1, 2 and 4 versus the logarithm of the viscosity of the medium shows a substantial increase of this ratio which corresponds mainly to the increase of the SW emission intensity, the effect on the LW emission being only moderate. As the pressure is increased, the rotation of the N-phenyl group of compound 1 is progressively hindered and the prevailing emission comes from a state which has the same geometry as the ground state (in which the planes of the two moieties of the molecule form an angle close to 60°). The effect is different when an electron-donating methoxy group is attached in the para position to the N-phenyl ring, compound 5, as mainly the LW fluorescence intensity increases with pressure. For this molecule which has an electron-donating p-substituent on the N-phenyl ring, the two moieties of the ground state molecule have a more planar geometry (43° angle) and the LW fluorescence appears to originate from an intramolecular charge transfer state the fluorescence of which increases with pressure. A three-level reaction scheme is proposed to account for the observed kinetics. In all cases, the viscosity of the medium is found to be the main factor which induces the changes in the fluorescence spectra, and the deceleration of the non-radiative deactivation from the SW* excited state is responsible for these modifications whether a reversible process between the two emitting SW* and LW* states is observed (as for compounds 2 and 4) or not (as for compound 1).

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. J. P. Launay, Computations for the Nano-Scale, ed. P. E. Blöchl, Kluwer Academic Publishers, Netherlands, 1993, p. 177.

  2. J. P. Launay, Molecular Electronics. Science and Technology, ed. A. Aviram, Engineering Foundation, New York, 1989, p. 237.

  3. A. Gourdon, J. P. Launay, M. Bujoli-Doeuff, F. Heisel, J. A. Miehé, E. Amouyal and M. L. Boillot, Twisted internal charge transfer (TICT) effect in bis(4-cyanophenyl)piperazine, a pseudo-dimer of dimethylaminobenzonitrile: A comparative study, J. Photochem. Photobiol. A: Chem., 1993, 71, 13–25.

    Article  CAS  Google Scholar 

  4. E. Lippert, W. Lüder and H. Boos, Advances in Molecular Spectroscopy, ed. A. Mangini, Pergamon Press, London, 1962, p. 443.

  5. E. Lippert, W. Lüder, F. Moll, W. Nägele, H. Boos, H. Progge and I. Seibold-Blankenstein, Umwandlung von Elektronenanregungsenergie, Angew. Chem., 1961, 21, 695–706.

    Article  Google Scholar 

  6. E. Lippert, Spektroskopische Bestimmung des Dipolmomentes aromatischer Verbindungen im ersten angeregten Singulettzustand, Z. Elektrochem., 1957, 61, 962–975.

    CAS  Google Scholar 

  7. J. Dobkowski, Z. R. Grabowski, J. Jasny and Z. Zielinski, Picosecond transient absorption spectra and the twisted intramolecular charge transfer phenomenon, Acta Phys. Pol. A, 1995, 88, 455–468.

    Article  CAS  Google Scholar 

  8. Z. R. Grabowski, Electron transfer in flexible molecules and molecular ions, Pure Appl. Chem., 1993, 65, 1751–1756.

    Article  CAS  Google Scholar 

  9. Z. R. Grabowski, K. Rotkiewicz, A. Siemiarczuk, D. J. Cowley and W. Braumann, Twisted intra-molecular charge-transfer states (TICT) — New class of excited-states with a full charge separation, Nouv. J. Chim., 1979, 3, 443–454.

    CAS  Google Scholar 

  10. K. Rotkiewicz, K. H. Grellman and Z. R. Grabowski, Reinterpretation of the anomalous fluorescence of p-N,N-dimethylamino-benzonitrile, Chem. Phys. Lett., 1973, 19, 315–318.

    Article  CAS  Google Scholar 

  11. W. Rettig and R. Lapouyade, Topics in Fluorescence Spectroscopy: Probe Design and Chemical Sensing, ed. J. R. Lakowicz., Plenum Press, New York, 1994, vol. 4, p. 109.

    Article  CAS  Google Scholar 

  12. W. Rettig, Charge separation in excited states of decoupled systems — TICT compounds and implications regarding the development of new laser dyes and the primary processes of vision and photosynthesis, Angew. Chem., Int. Ed. Engl., 1986, 25, 971–988.

    Article  Google Scholar 

  13. G. Scholes, D. Phillips and I. R. Gould, Book of Abstracts of the XVIth IUPAC Symposium on Photochemistry, Helsinki, July 1996, p. 513.

    Google Scholar 

  14. G. D. Scholes, D. Phillips and I. R. Gould, Low-lying excited states of 4-dimethylaminobenzonitrile: equilibrium geometries, vibrational frequencies and charge transfer character, Chem. Phys. Lett., 1997, 266, 521–526.

    Article  CAS  Google Scholar 

  15. T. von der Haar, A. Hebecker, Y. Il’ichev, Y.-B. Jiang, W. Kühnle and K. A. Zachariasse, Excited-state intramolecular charge transfer in donor/acceptor-substituted aromatic hydrocarbons and in biaryls. The significance of the redox potentials of the D/A, Recl.: Trav. Chim. Pays-Bas, 1995, 114, 430–442.

    Google Scholar 

  16. K. A. Zachariasse, T. von der Haar, U. Leinhos and W. Kühnle, Solvent-induced pseudo-Jahn–Teller coupling in dual fluorescence. Evidence against the TICT hypothesis, J. Inf. Rec. Mater., 1994, 21, 501–506.

    CAS  Google Scholar 

  17. K. A. Zachariasse, T. von der Haar, A. Hebecker, U. Leinhos and W. Kühnle, Intramolecular charge transfer in aminobenzonitriles: requirements for dual fluorescence, Pure Appl. Chem., 1993, 65, 1745–1750.

    Article  CAS  Google Scholar 

  18. A. Demeter, T. Bérces, L. Biczók, V. Wintgens, P. Valat and J. Kossanyi, Comprehensive model of the photophysics of N-phenylnaphthalimides: The role of solvent and rotational relaxation, J. Phys. Chem., 1996, 100, 2001–2011.

    Article  CAS  Google Scholar 

  19. P. Valat, V. Wintgens, J. Kossanyi, L. Biczók, A. Demeter and T. Bérces, Influence of geometry on the emitting properties of 2,3-naphthalimides, J. Am. Chem. Soc., 1992, 114, 946–953.

    Article  CAS  Google Scholar 

  20. V. Wintgens, P. Valat, J. Kossanyi, L. Biczók, A. Demeter and T. Bérces, Spectroscopic properties of aromatic dicarboximides. Part 1: N-H and N-methyl-substituted naphthalimides, J. Chem. Soc., Faraday Trans., 1994, 90, 411–421.

    Article  CAS  Google Scholar 

  21. H. Lueck, M. W. Windsor and W. Rettig, Pressure dependence of the kinetics of photoinduced intramolecular charge separation in 9,9′-bianthryl monitored by picosecond transient absorption: comparison with electron transfer in photosynthesis, J. Phys. Chem., 1990, 94, 4550–4559.

    Article  CAS  Google Scholar 

  22. J. Y. Liu and J. R. Bolton, Intramolecular photochemical electron transfer. 7. Temperature dependence of electron-transfer rates in covalently linked porphyrin-amide-quinone molecules, J. Phys. Chem., 1992, 96, 1718–1725.

    Article  CAS  Google Scholar 

  23. Landolt-Börnstein, Zahlenwerte und Funktionen aus Physik, Chemie, Astronomie, Geophysik und Technik, Bd. 2: Eigenschaften der Materie in ihren Aggregatzuständen, Springer Verlag, Berlin, 1959, vol. 6 and 8.

  24. P. Valat, V. Wintgens, J. Kossanyi, L. Biczók, A. Demeter and T. Bérces, Temperature-dependent behaviour of the dual fluorescence of 2-(3-fluorophenyl)-2,3-dihydro-1H-benzo[f]isoindole-1,3-dione, Helv. Chim. Acta, 2001, 84, 2813–2832.

    Article  CAS  Google Scholar 

  25. K. Heger, M. Uematsu and E. U. Franck, The static dielectric constant of water at high pressures and temperatures to 500 MPa and 550 0C, Ber. Bunsen-Ges. Phys. Chem., 1980, 84, 758–762.

    Article  CAS  Google Scholar 

  26. E. Groubert and E. Charles, Development of a viscosity coefficient for shearing stress in glycerol and its acetates as a function of pressure, C. R. Acad. Sci., Ser. C, 1969, 269, 1454–1458.

    CAS  Google Scholar 

  27. Owen and Brinckley, Physico-Chemical Effects of Pressure, ed. S. D. Hermann, Butterworth Scientific Publications, London, 1957, p. 103.

  28. D. H. Waldeck and G. R. Fleming, Influence of viscosity and temperature on rotational reorientation. Anisotropic absorption studies of 3,3′-diethyloxa-dicarbocyanine iodide, J. Phys. Chem., 1981, 85, 2614–2617.

    Article  CAS  Google Scholar 

  29. L. A. Phillips, S. P. Webb and J. H. Clark, High-pressure studies of rotational reorientation dynamics; The role of dielectric friction, J. Phys. Chem., 1985, 83, 5810–5821.

    Article  Google Scholar 

  30. V. Wintgens, P. Valat, J. Kossanyi, A. Demeter, L. Biczók and T. Bérces, Spectroscopic properties of aromatic dicarboximides. Part 3: Substituent effect on the photophysical properties of N-phenyl-2,3-napthalimides, J. Photochem. Photobiol. A: Chem., 1996, 93, 109–117.

    Article  CAS  Google Scholar 

  31. S. Tripathi, M. Simalty, J. Pouliquen and J. Kossanyi, Préparations, propriétés spectroscopiques et électrochimiques de sels de pyrylium à structure bloquée, Bull. Soc. Chim. Fr., 1986, 600–612.

    Google Scholar 

  32. G. Hui Bon Hoa, C. Di Primo, I. Dondaine, S. G. Sligar, I. C. Gunsalus and P. Douzou, Conformational changes of cytochromes P-450cam and P-450lin induced by high pressure, Biochemistry, 1989, 28, 651–656.

    Article  CAS  PubMed  Google Scholar 

  33. G. Hui Bon Hoa, P. Douzou, N. Dahan and C. Balny, High-Pressure Spectrometry at Subzero Temperatures, Anal. Biochem., 1982, 120, 125–135.

    Article  CAS  PubMed  Google Scholar 

  34. G. A. von Salis and H. Labhart, Temperature dependence of the viscosity of organic glasses, J. Phys. Chem., 1968, 72, 752–754.

    Article  Google Scholar 

  35. Y. Dromzée, J. Kossanyi, V. Wintgens, P. Valat, L. Biczók, A. Demeter and T. Bérces, Crystal and molecular structure of N-phenyl substituted 1,2-, 2,3- and 1,8-naphthalimides, Z. Kristallogr., 1995, 210, 760–765.

    Article  Google Scholar 

  36. H. H. Jaffé, A Reexamination of the Hammett Equation, Chem. Rev., 1953, 53, 191–261.

    Article  Google Scholar 

  37. H. C. Brown and Y. Okamoto, Directive effects in aromatic substitution. 30. Electrophilic substituent constants, J. Am. Chem. Soc., 1958, 80, 4979–4987.

    Article  CAS  Google Scholar 

  38. Z. A. Dreger, J. M. Lang and H. G. Drickamer, Pressure- and light-induced luminescence of several aldehydes dissolved in polymer matrices, J. Phys. Chem., 1996, 100, 4646–4653.

    Article  CAS  Google Scholar 

  39. Z. A. Dreger, J. M. Lang and H. G. Drickamer, I. Julolidinemalononitrile, High pressure study of flexible fluorescent dye molecules in solid polymeric media, Chem. Phys., 1993, 169, 351–359.

    Article  CAS  Google Scholar 

  40. K. Hara and W. Rettig, Effect of pressure on the fluorescence of TICT states in (N,N-dimethylamino)benzonitrile and related compounds, J. Phys. Chem., 1992, 96, 8307–8309.

    Article  CAS  Google Scholar 

  41. K. Hara, T. Arase and J. Osugi, Effect of high-pressure on intramolecular electron-transfer luminescence of 9,9′-biantryl in different solvents, J. Am. Chem. Soc., 1984, 106, 1968–1972.

    Article  CAS  Google Scholar 

  42. K. Yamasaki, K. Arita, O. Kajimoto and K. Hara, The torsional potential of 9,9′-bianthryl determined by laser-induced fluorescence in a free jet, Chem. Phys. Lett., 1986, 123, 277–281.

    Article  CAS  Google Scholar 

  43. L. R. Khundkar and A. H. Zewail, Excition and vibronic effects in the spectroscopy of bianthracene in supersonic beams, J. Chem. Phys., 1986, 84, 1302–1311.

    Article  CAS  Google Scholar 

  44. Z. R. Grabowski and J. Dobkowski, Charge-transfer (TICT) excited-states-energy and molecular-structure, Pure Appl. Chem., 1983, 55, 245–252.

    Article  CAS  Google Scholar 

  45. W. Rettig and M. Zander, Broken symmetry in excited-states of 9,9′-biantryl, Ber. Bunsen-Ges. Phys. Chem., 1983, 87, 1143–1149.

    Article  CAS  Google Scholar 

  46. K. R. Srinivasan and R. L. Kay, Pressure-dependence of dielectric-constant and density of acetonitrile at 3 temperatures, J. Solution Chem., 1977, 6, 357–367.

    Article  CAS  Google Scholar 

  47. W. Rettig, in Modern Models of Bonding and Delocalization, ed. J. Liebman and A. Greenberg, VCH Publishers, New York, 1988, ch. 5.

  48. J. Heldt and M. Kasha, Dielectric medium interaction in proton-transfer and charge-transfer molecular electronic excitation, J. Mol. Liquids, 1989, 41, 305–313.

    Article  CAS  Google Scholar 

  49. E. Lippert, Photophysics of internal twisting II. Fluorescence spectroscopic studies of horizontal transitions, Ber. Bunsen-Ges. Phys. Chem., 1988, 92, 417–422.

    Article  CAS  Google Scholar 

  50. W. Rettig, in Fluorescence Spectroscopy. New Methods and Applications, ed. O. S. Wolfbeis, Springer Verlag, Berlin, 1993, p. 31.

  51. K. Rotkiewicz and W. Rettig, The TICT excited state of secondary aromatic amines, J. Lumin., 1992, 54, 221–229.

    Article  CAS  Google Scholar 

  52. M. Vogel and W. Rettig, Efficient intramolecular fluorescence quenching in triphenylmethane-dyes involving excited states with charge separation and twisted conformations, Ber. Bunsen-Ges. Phys. Chem., 1985, 89, 962–968.

    Article  CAS  Google Scholar 

  53. Y. Dromzée and J. Kossanyi, unpublished results

  54. R. Englman and J. Jortner, The energy gap law for radiationless transitions in large molecules, Mol. Phys., 1970, 18, 145–164.

    Article  CAS  Google Scholar 

  55. J. M. Lang, Z. A. Dreger and H. G. Drickamer, A high pressure study of the effect of viscosity on the light induced isomerization of DMABN in three linear alcohols, iso-butanol and glycerol, Chem. Phys. Lett., 1995, 243, 78–84.

    Article  CAS  Google Scholar 

  56. F. Lahmani, P. Valat and J. Kossanyi, Properties of pyrilium-salts having a free-rotating ortho-anisyl and meta-anisyl substituent, New J. Chem., 1995, 19, 965–977.

    Google Scholar 

  57. M. Van der Auweraer, Z. R. Grabowski and W. Rettig, Molecular structure and temperature-dependent radiative rates in twisted intramolecular charge transfer and exciplex systems, J. Phys. Chem., 1991, 95, 2083–2092.

    Article  Google Scholar 

  58. R. Menzel, H. Lueck, K. Jordan and M. W. Windsor, Pressure-dependence of the conformational relaxation process in the excited-state of tetramethyl-paraterphenyl in solution, Chem. Phys. Lett., 1988, 145, 61–66.

    Article  CAS  Google Scholar 

  59. H. A. Kramers, Brownian motion in a field of force and the diffusion model of chemical reactions, Physica (Amsterdam), 1940, 7, 284–304.

    Article  CAS  Google Scholar 

  60. B. Bagchi, Isomerization dynamics in solution, Int. Rev. Phys. Chem., 1987, 6, 1–34.

    Article  CAS  Google Scholar 

  61. J. T. Edward, Molecular volumes and the Stokes–Einstein equation, J. Chem. Educ., 1970, 47, 261–270.

    Article  CAS  Google Scholar 

  62. F. Lòpez-Arbeloa, I. Urrecha-Aguirresacona and I. Lòpez-Arbeloa, Influence of the molecular structure and the nature of the solvent on the absorption and fluorescence characteristics of rhodamines, Chem. Phys., 1989, 130, 371–378.

    Article  Google Scholar 

  63. F. Lòpez-Arbeloa, T. Lòpez-Arbeloa, P. Hernandez-Bartolomé, M. J. Tapia-Estévez and I. Lòpez-Arbeloa, Proc. Indian Acad. Sci., 1992, 104, 165–171.

    Google Scholar 

  64. D. Phillips, Intramolecular charge-transfer studied by time-resolved vibrational spectroscopies, The Spectrum, 2002, 15, 8–12.

    CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Institut de Biologie Physico-Chimique, U310-INSERM, 13 rue Pierre et Marie Curie, 75005 -, Paris, France

    Gaston Hui Bon Hoa

  2. Laboratoire de Recherche sur les Polymères, C.N.R.S., 2-8 rue Henri Dunant, 94320 -, Thiais, France

    Jean Kossanyi

  3. Institute of Chemistry, Chemical Research Center of the Hungarian Academy of Sciences, Pusztaszeri ùt 59-67, 1025 -, Budapest, Hungary

    Attila Demeter, László Biczók & Tibor Bérces

Authors
  1. Gaston Hui Bon Hoa
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Jean Kossanyi
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Attila Demeter
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. László Biczók
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Tibor Bérces
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Jean Kossanyi.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Hoa, G.H.B., Kossanyi, J., Demeter, A. et al. Pressure dependence of the dual luminescence of twisting molecules. The case of substituted 2,3-naphthalimides. Photochem Photobiol Sci 3, 473–482 (2004). https://doi.org/10.1039/b313804f

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1039/b313804f

Search

Navigation