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Effect of oligothiophene substituents on the photophysical and photochromic properties of a naphthopyran

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Abstract

A spectrokinetic study of the photophysical and photochemical properties of a series of photochromes bearing thienyl (T1), dithienyl (T2) and terthienyl (T3) groups linked to a naphthopyran in position 3 (sp3 carbon) or 8 (naphtho moiety) has been carried out. The effect of the number and position of the thienyl groups on the excited state properties of the six compounds in the singlet and triplet manifold has been investigated by stationary and pulsed fluorimetric techniques, laser flash photolysis and kinetic analysis of the colouration/decolouration processes upon continuous irradiation. On increasing the length of the oligothiophene moiety, the contribution of fluorescence to the deactivation processes becomes detectable, while the photocolouration yield decreases. Moreover, only for compounds with T3 groups was the triplet absorption observed by laser flash photolysis; its decay did not contribute to photocolouration. The competition between physical (fluorescence emission and intersystem crossing) and chemical relaxations markedly affects the behaviour of the compound bearing the T3 group at the naphtho moiety, which shows the most efficient intersystem crossing and fluorescence emission while does not lead to photoproduction of the coloured open form. A parallel study of the NMR spectra of the compounds bearing one thiophene group allowed two and four photomerocyanine-type photoproducts to be identified for the naphtho-substituted and pyran-substituted compounds, respectively. The compound with a thiophene group at the naphtho moiety was studied in more detail at different temperatures. On the basis of the combined optical and NMR spectrometric results, a reasonable mechanism of its photochromic behaviour is proposed.

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References

  1. J. C. Crano and R. J. Guglielmetti, Organic Photochromic and Thermochromic Compounds, Kluwer Academic–Plenum Publishers, New York, 1999, vol. 1–2

  2. H. Dürr and H. Bouas-Laurent, Photochromism: Molecules and Systems, Elsevier, Amsterdam, 1990.

    Google Scholar 

  3. G. J. Ashwell, Molecular Electronics, John Wiley & Sons Inc., New York, 1992

    Google Scholar 

  4. G. Berkovic, V. Krongauz and V. Weiss, Spyropyrans and spirooxazines for memories and switches, Chem. Rev., 2000, 100, 1741–1753

    Google Scholar 

  5. S. Kawata and Y. Kawata, Three-dimensional optical data storage using photochromic materials, Chem. Rev., 2000, 100, 1777–1788.

    Google Scholar 

  6. J. Roncali, Chem. Rev., 1992, 92, 711–738

    Google Scholar 

  7. J. Roncali, Chem. Rev., 1997, 97, 173–205

    Google Scholar 

  8. M. Frigoli, C. Moustrou, A. Samat and R. Guglielmetti, Photomodulable materials. Synthesis and properties of photochromic 3H-naphtho[2,1-b]pyrans linked to thiophene units via an acetylenic junction, Helv. Chim. Acta, 2000, 83, 3043–3052

    Google Scholar 

  9. F. Ortica, C. Moustrou, J. Berthet, G. Favaro, A. Samat, R. Guglielmetti, G. Vermeersch and U. Mazzucato, Comprehensive photokinetic and NMR study of a biphotochromic supermolecule involving two naphthopyrans linked to a central thiophene unit through acetylenic bonds, Photochem. Photobiol., 2003, 78, 558–566.

    Google Scholar 

  10. N. Rebiere, C. Moustrou, M. Meyer, A. Samat, R. Guglielmetti, J.-C. Micheau and J. Aubard, Structure–property relationships in a series of photochromic thiophene-substituted 3H-naphtho[2,1-b]pyrans, J. Phys. Org. Chem., 2000, 13, 523–530

    Google Scholar 

  11. S. Coen, C. Moustrou, M. Frigoli, M. Julliard, A. Samat and R. Guglielmetti, Spectroscopic properties of thiophene-linked [2H]-chromenes, J. Photochem. Photobiol. A: Chem., 2001, 139, 1–4

    Google Scholar 

  12. A. Yassar, N. Rebière-Galy, M. Frigoli, C. Moustrou, A. Samat and R. Guglielmetti, Molecular photo switch based on photochromic oligothiophenes, Synth. Met., 2001, 121, 1463–1464

    Google Scholar 

  13. M. Frigoli, V. Pimienta, C. Moustrou, A. Samat, R. Guglielmetti, J. Aubard, F. Maurel, J.-C. Micheau, Continuous irradiation and flash-photolysis studies of new [3H]naphtho[2,1-b]pyrans linked by covalent bonds to oligothiophene units. Effect of thiophene substituents on the photochromism, Photochem. Photobiol. Sci., 2003, 2, 888–892.

    Google Scholar 

  14. S. Delbaere, C. Bochu, N. Azaroual, G. Buntinx and G. Vermeersch, NMR studies of the structure of the photoinduced forms of photochromic spironaphthoxazines, J. Chem. Soc., Perkin Trans. 2, 1997, 1499–1502

    Google Scholar 

  15. S. Delbaere, B. Luccioni-Houze, C. Bochu, Y. Teral, M. Campredon and G. Vermeersch, Kinetic and structural studies of the photochromic process of 3H-naphthopyrans by UV and NMR spectroscopy, J. Chem. Soc., Perkin Trans. 2, 1998, 1153–1158

    Google Scholar 

  16. S. Delbaere, J.-C. Micheau, Y. Teral, C. Bochu, M. Campredon and G. Vermeersch, NMR structural and kinetic assignment of fluoro-3H-naphthopyran photomerocyanines, Photochem. Photobiol., 2001, 74, 694–699.

    Google Scholar 

  17. G. Bartocci, F. Masetti, U. Mazzucato, A. Spalletti, I. Baraldi and F. Momicchioli, Photophysical and theoretical studies of photoisomerism and rotamerism of trans-styrylphenanthrenes, J. Phys. Chem., 1987, 91, 4733–4743.

    Google Scholar 

  18. S. L. Murov, I. Carmichael and G. L. Hug, Handbook of Photochemistry, Marcel Dekker Inc., New York, 1993.

    Google Scholar 

  19. C. V. Kumar, L. Qin and P. K. Das, Aromatic thioketone triplets and their quenching behaviour towards oxygen and di-t-butylnitroxy radical, J. Chem. Soc., Faraday Trans. 2, 1984, 80, 783–793.

    Google Scholar 

  20. G. Ottavi, G. Favaro and V. Malatesta, Spetrokinetic study of 2,2-diphenyl-5,6-benzo(2H)chromene: a thermoreversible and photoreversible photochromic system, J. Photochem. Photobiol. A: Chem., 1998, 115, 123–128.

    Google Scholar 

  21. R. S. Becker, J. Seixas de Melo, A. L. Maçanita and F. Elisei, Comprehensive investigation of the solution photophysics and theoretical aspects of oligothiophenes of 1–7 rings, Pure Appl. Chem., 1995, 67, 9–16

    Google Scholar 

  22. R. S. Becker, J. Seixas de Melo, A. L. Maçanita and F. Elisei, Comprehensive evaluation of the absorption, photophysical, energy transfer, structural, and theoretical properties of α-oligothiophenes with one to seven rings, J. Phys. Chem., 1996, 100, 18683–18695.

    Google Scholar 

  23. R. S. Becker, E. Dolan and D. E. Balke, Vibronic effects in photochemistry. Competition between internal conversion and photochemistry, J. Chem. Phys., 1969, 50, 239–245

    Google Scholar 

  24. R. S. Becker, A. P. Pelliccioli, A. Romani and G. Favaro, Vibronic quantum effects in fluorescence and photochemistry. Competition between vibrational relaxation and photochemistry and consequences on photochemical control, J. Am. Chem. Soc., 1999, 121, 2104–2109.

    Google Scholar 

  25. H. Görner and A. K. Chibisov, Photoprocess in 2,2-diphenyl-5,6 benzo(2H)chromene, J. Photochem. Photobiol., A: Chem., 2002, 149, 83–89.

    Google Scholar 

  26. J. Hobley, V. Malatesta, R. Millini, W. Giroldini, L. Wis, M. Goto, M. Kishimoto and H. Fukumura, Photochromism of chromene crystals; a new property of old chromenes, Chem. Commun., 2000, 1339–1340.

    Google Scholar 

  27. J. Aubard, F. Maurel, G. Buntinx, O. Poizat, G. Levi, R. Guglielmetti and A. Samat, Femto/pico transient absorption spectroscopy of photochromic 3,3-diphenylnaphtho[2,1-b]pyran, Mol. Cryst. Liq. Cryst., 2000, 345, 215–220.

    Google Scholar 

  28. S. Delbaere, J.-C. Micheau and G. Vermeersch, NMR kinetic investigations of the photochemical and thermal reactions of a photochromic chromene, J. Org. Chem., 2003, 68, 8968–8973.

    Google Scholar 

  29. G. Ottavi, F. Ortica and G. Favaro, Photokinetic methods: a mathematical analysis of the rate equations in photochromic systems, Int. J. Chem. Kin., 1999, 31, 303–313.

    Google Scholar 

  30. G. Favaro, A. Romani and R. S. Becker, Photochromic behavior of 2,2-spiro-adamantylidene-2H-naphtho[1,2-b]pyran: a new thermoreversible and photoreversible photochromic system, Photochem. Photobiol., 2000, 72, 632–638.

    Google Scholar 

  31. F. Ortica and G. Favaro, Effect of gel trapping on spectral properties and relaxation dynamics of some spiro-oxazines, J. Phys. Chem. B., 2000, 104, 12179–12183.

    Google Scholar 

  32. S. Delbaere and G. Vermeersch, NMR proofs of the involvement of an allenyl-naphthol as a key-intermediate in the photochromic process of [3H]-naphthopyrans, Tetrahedron Lett., 2003, 44, 259–262

    Google Scholar 

  33. S. Delbaere, J.-C. Micheau and G. Vermeersch, Multinuclear NMR structural characterization of an unprecedented photochromic allene intermediate, Org. Lett., 2002, 4, 3143–3145

    Google Scholar 

  34. S. Delbaere and G. Vermeersch, NMR characterization of allenyl-naphthol in the photochromic process of 3,3-diphenyl-[3H]-naphtho[2–1,b]pyran, J. Photochem. Photobiol., A: Chem., 2003, 159, 227–232.

    Google Scholar 

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Authors and Affiliations

  1. Dipartimento di Chimica, Università di Perugia, 06123, Perugia, Italy

    Fausto Ortica, Paola Smimmo, Gianna Favaro & Ugo Mazzucato

  2. Faculté de Pharmacie, Université de Lille 2, UMR CNRS 8009, F-59006, Lille Cedex, France

    Stéphanie Delbaere, David Venec & Gaston Vermeersch

  3. Faculté des Sciences de Luminy, Université de la Méditerranée, UMR CNRS 6114, 13288, Marseille Cedex 9, France

    Michel Frigoli, Corinne Moustrou & André Samat

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  1. Fausto Ortica
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  2. Paola Smimmo
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  3. Gianna Favaro
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  5. Stéphanie Delbaere
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Ortica, F., Smimmo, P., Favaro, G. et al. Effect of oligothiophene substituents on the photophysical and photochromic properties of a naphthopyran. Photochem Photobiol Sci 3, 878–885 (2004). https://doi.org/10.1039/b406801g

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