Skip to main content
SpringerLink
Log in

Photochemistry of 2-(4-hydroxystyryl)-1-naphthopyrylium

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

Abstract

A new photochromic system based on 2-(4-hydroxystyryl)-1-naphthopyrylium encompasses the properties of the previously described naphthoflavylium and styrylflavylium systems. The photoproduct exhibits a colour deep in hue and is red shifted in comparison with the equivalent flavylium system. Reaction of 2-hydroxy-1-naphthaldehyde with p-hydroxystyrylmethylketone in acetic acid in the presence of tetrafluoroboric acid and acetic anhydride as catalysts leads to a mixture of two compounds: the photochromic 2-(4-hydroxystyryl)-1-naphthopyrylium and a second product 2-(4-acetoxystyryl)-1-naphthopyrylium resulting from the acetylation by acetic anhydride of the former. In acidic medium and at room temperature the hydrolysis of the acetoxy derivative leads to the 2-(4-hydroxystyryl)-1-naphthopyrylium, in circa 2 days, [HCl] = 0.25 M. The pH dependent chemical reactions taking place with 2-(4-hydroxystyryl)-1-naphthopyrylium were determined by UV-Vis, stooped flow, flash photolysis and 1H NMR and follow the same general pattern of flavylium derivatives. In order to rationalize the photochromism, an energy level diagram summarizing all the equilibrium and rate constants of the network was drawn.

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

Notes and references

  1. R. Brouillard and J.-E. Dubois, Mechanism of structural transformations of anthocyanins in acidic medium, J. Am. Chem. Soc. 1977, 99, 1359–1364.

    Article  CAS  Google Scholar 

  2. R. Brouillard and B. Delaporte, Chemistry of anthocyanins pigments. 2. Kinetic and thermodynamic study of proton transfer, hydration and tautomerization reactions of malvidin 3-glucoside, J. Am. Chem. Soc. 1977, 99, 8461–8468.

    Article  CAS  Google Scholar 

  3. R. Brouilard, B. Delaporte and J.-E. Dubois, Chemistry of anthocyanin pigments. 3. Relaxation amplitudes in pH jumps experiments, J. Am. Chem. Soc. 1978, 100, 6202–6205.

    Article  Google Scholar 

  4. F. Pina, Thermodynamic and kinetics of flavylium salts. Malvin revisited, J. Chem. Soc., Faraday Trans. 1998, 94, 2109–2116. Correction 1998, 94, 3781–3781

    Article  CAS  Google Scholar 

  5. R. Brouillard and J. Lang, The hemiacetal–cis-chalcone equilibrium of malvin, a natural anthocyanin, Can. J. Chem. 1990, 68, 755–761.

    Article  CAS  Google Scholar 

  6. F. Pina, M. J. Melo, C. A. T. Laia, A. J. Parola and J. C. Lima, Chemistry and applications of flavylium compounds: a handful of colours, Chem. Soc. Rev. 2012, 41, 869–908.

    Article  CAS  Google Scholar 

  7. R. Gomes, A. M. Diniz, A. Jesus, A. J. Parola and F. Pina, The synthesis and reaction network of 2-styryl-1-benzopyrylium salts: an unexploited class of potential colorants, Dyes Pigm. 2009, 81, 69–79.

    Article  CAS  Google Scholar 

  8. A. M. Diniz, R. Gomes, A. J. Parola, C. A. T. Laia and F. Pina, Photochemistry of 7-hydroxy-2-(4-hydroxystyryl)-1-benzopyrylium and related compounds, J. Phys. Chem. B 2009, 113, 719–727.

    Article  CAS  Google Scholar 

  9. R. Gavara, V. Petrov and F. Pina, Characterization of the 4’-hydroxynaphthoflavylium network of chemical reactions, Photochem. Photobiol. Sci. 2010, 9, 298–303.

    Article  CAS  Google Scholar 

  10. R. Gavara, V. Petrov, V. Lopez and F. Pina, Photochromism of naphthoflavylium. On the role of the hemiketal B4, J. Photochem. Photobiol., A: Chemistry 2011, 220, 4–10.

    Article  CAS  Google Scholar 

  11. A. R. Katritzky, P. Czerney, J. R. Levell and W. H. Du, Molecular engineering of benzo[ b]pyrylium salts by indirect electrophilic substitution, Eur. J. Org. Chem. 1998 2623–2629.

    Google Scholar 

  12. H. E. Gottlieb, V. Kotlyar and A. Nudelman, NMR chemical shifts of common laboratory solvents as trace impurities, J. Org. Chem. 1997, 62, 7512–7515.

    Article  CAS  Google Scholar 

  13. See for example: L. F. Wang, L. Q. Kong, L. Fan and D. C. Yang, Facile synthesis of chiral N-glycosylated amino acids, Res. Chem. Intermed. 2010, 36, 237–243.

    Article  CAS  Google Scholar 

  14. P. F. Moreira Jr., L. Giestas, C. Yihwa, C. Vautier-Giongo, F. H. Quina, A. L. Maçanita and J. C. Lima, Ground- and excited-state proton transfer in anthocyanins: from weak acids to superphotoacids, J. Phys. Chem. A 2003, 107, 4203–4210.

    Article  CAS  Google Scholar 

  15. A. A. Freitas, F. H. Quina, A. A. L. Maçanita, Picosecond dynamics of proton transfer of a 7-hydroxyflavylium salt in aqueous-organic solvent mixtures, J. Phys. Chem. A 2011, 115, 10988–10995.

    Article  CAS  Google Scholar 

  16. F. Galindo, J. C. Lima, S. V. Luis, M. J. Melo, A. J. Parola and F. Pina, Water/humidity and ammonia sensor, based on a polymer hydrogel matrix containing a fluorescent flavylium compound, J. Mater. Chem. 2005, 15, 2840–2847.

    Article  CAS  Google Scholar 

  17. G. Hauckle, P. Czerney, D. Steen, W. Rettig and H. Hartmann, Radiationless transitions in substituted benzopyrylium dyes: competing adiabatic photoreactions towards nonradiative funnels, Ber. Bunsen-Ges. Phys. Chem. 1993, 97, 561–570.

    Article  Google Scholar 

  18. M. Elhabiri, P. Figueiredo, F. George, J.-P. Cornard, A. Fougerousse, J.-C. Merlin and R. Brouillard, Ground- and excited-state properties of some naphthoflavyliums, Can. J. Chem. 1996, 74, 697–706.

    Article  CAS  Google Scholar 

  19. P. Figueiredo, J. C. Lima, H. Santos, M. C. Wigand, R. Brouillard, A. L. Maçanita and F. Pina, Photochromism of the synthetic 4’,7-dihydroxyflavylium chloride, J. Am. Chem. Soc. 1994, 116, 1249–1254.

    Article  CAS  Google Scholar 

  20. F. Pina, A. Roque, M. J. Melo, M. Maestri, L. Belladelli and V. Balzani, Multistate/multifunctional molecular-level systems: light and pH switching between the various forms of a synthetic flavylium salt, Chem.–Eur. J. 1998, 4, 1184–1191.

    Article  CAS  Google Scholar 

  21. The terms flavylium cation, quinoidal base, hemiketal and chalcones are used by commodity. Actually they are naphthostyryl derivatives

  22. R. A. Mcclelland and S. Gedge, Hydration of the flavylium ion, J. Am. Chem. Soc. 1980, 102, 5838–5848.

    Article  CAS  Google Scholar 

  23. Y. Leydet, A. J. Parola and F. Pina, Hydroxypyrydinechromene and pyridinechalcone: two coupled photochromic systems, Chem.–Eur. J. 2010, 16, 545–555.

    Article  CAS  Google Scholar 

  24. F. Pina, M. J. Melo, M. Maestri, R. Ballardini and V. Balzani, Photochromism of 4’-methoxyflavylium perchlorate. a “write-lock-read-unlock-erase” molecular switching system, J. Am. Chem. Soc. 1997, 119, 5556–5561.

    Article  CAS  Google Scholar 

  25. H. Duerr and H. Bouas-Laurent, Photochromism: Molecules and Systems, Elsevier, Amsterdam, 2003.

    Google Scholar 

  26. M. Heilemann, P. Dedecker, J. Hofkens and M. Sauer, Photoswitches: key molecules for subdifraction-resolution fluorescence imaging and molecular quantification, Laser Photonics Rev. 2009, 3, 180–202.

    Article  CAS  Google Scholar 

  27. F. W. Küster and A. Thiel, Tabelle per le Analisi Chimiche e Chimico-Fisiche, Hoepli, Milano, 12th edn, 1982, pp. 157–160.

    Google Scholar 

  28. F. Pina, M. J. Melo, R. Ballardini, L. Flamigni and M. Maestri, Flash photolysis of 4’,7’-dihydroxyflavylium, New J. Chem. 1997, 21, 969–976.

    CAS  Google Scholar 

  29. C. G. Hatchard and C. A. Parker, A new sensitive chemical actinometer. 2. Potassium ferrioxalate as a standard actinometer, Proc. R. Soc. London, Ser. A 1956, 235, 518–536.

    CAS  Google Scholar 

  30. L. Porrès, A. Holland, L.-O. Pålsson, A. P. Monkman, C. Kemp and A. Beeby, Absolute measurements of photoluminescence quantum yields of solutions using an integrating sphere, J. Fluoresc. 2006, 16, 267–272.

    Article  Google Scholar 

  31. R. A. McClelland and G. H. McGall, The 4’-hydroxyflavylium ion, J. Org. Chem. 1982, 47, 3730–3736.

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Departamento de Química, Faculdade de Ciências e Tecnologia, REQUIMTE, 2829-516, Caparica, Portugal

    Raquel Gavara, Yoann Leydet, Vesselin Petrov & Fernando Pina

Authors
  1. Raquel Gavara
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Yoann Leydet
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Vesselin Petrov
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Fernando Pina
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Fernando Pina.

Additional information

This article is published as part of a themed issue in honour of Jean-Pierre Desvergne on the occasion of his 65th birthday.

Electronic supplementary information (ESI) available. See DOI: 10.1039/c2pp25104c

Rights and permissions

Reprints and permissions

About this article

Cite this article

Gavara, R., Leydet, Y., Petrov, V. et al. Photochemistry of 2-(4-hydroxystyryl)-1-naphthopyrylium. Photochem Photobiol Sci 11, 1691–1699 (2012). https://doi.org/10.1039/c2pp25104c

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1039/c2pp25104c

Search

Navigation