Skip to main content
SpringerLink
Log in

Photoexcited triplet states of new UV absorbers, cinnamic acid 2-methylphenyl esters

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

Abstract

Phosphorescence spectra of nonphosphorescent or very weakly phosphorescent new UV absorbers, 2-methylphenyl cinnamate (MePC), 2-methylphenyl 4-methoxycinnamate (MePMC) and 2-methyl-phenyl 4-ethoxycinnamate (MePEC) have been observed by using external heavy atom effects of ethyl iodide in ethanol at 77 K. The lowest excited triplet (T1) energies of these new UV absorbers are lower than those of a widely used UV-A absorber, 4-tert-butyl-4’-methoxydibenzoylmethane (BM-DBM), in both keto and enol forms. The intermolecular triplet-triplet energy transfer from photolabile BM-DBM to MePMC was observed by measuring the time-resolved phosphorescence spectra. Electron paramagnetic resonance spectra have been observed for the T1 states of these new UV absorbers in ethanol at 77 K by using benzophenone as a triplet sensitizer. The observed T1 lifetimes, zero-field splitting (ZFS) parameters and molecular orbital calculations of the ZFS parameters suggest that T1 states of these new UV absorbers posses mainly 3ππ* character. The deactivation processes of the lowest excited singlet (S1) states are predominantly fluorescence and internal conversion to the ground (G) states in MePMC and MePEC, while the main deactivation process of the S1 state of MePC is internal conversion to the G state. The molar absorption coefficients of MePMC and MePEC in the UV-A and UV-B regions are larger than that of most widely used UV-B absorber, octyl methoxycinnamate.

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. C. A. Bonda, The photostability of organic sunscreen actives: A review, in Sunscreens, ed. N. A. Shaath, Taylor & Francis, Boca Raton, 2005, pp. 321–349.

    Google Scholar 

  2. V. Lhiaubet-Vallet, M. Marin, O. Jimenez, O. Gorchs, C. Trullas and M. A. Miranda, Filter-filter interactions. Photostabilization, triplet quenching and reactivity with singlet oxygen, Photochem. Photobiol. Sci., 2010, 9, 552–558.

    Article  Google Scholar 

  3. S. Scalia and M. Mezzena, Photostabilization effect of quercetin on the UV filter combination, butyl methoxydibenzoylmethane-octyl methoxycinnamate, Photochem. Photobiol., 2010, 86, 273–278.

    Article  CAS  Google Scholar 

  4. C. Bonda, A. Pavlovic, K. Hanson and C. Bardeen, Singlet quenching proves faster is better for photostability, Cosmet. Toiletries, 2010, 125, 40–48.

    CAS  Google Scholar 

  5. B. Herzog, M. Wehrle and K. Quass, Photostability of UV absorber system in sunscreens, Photochem. Photobiol., 2009, 85, 869–878.

    Article  CAS  Google Scholar 

  6. C. Paris, V. Lhiaubet-Vallet, O. Jiménez, C. Trullas and M. A. Miranda, A blocked diketo form of avobenzone: Photostability, photosensitizing properties and triplet quenching by a triazine-derived UVB-filter, Photochem. Photobiol., 2009, 85, 178–184.

    Article  CAS  Google Scholar 

  7. C. Mendrok-Edinger, K. Smith, A. Janssen and J. Vollhardt, The quest for avobenzone stabilizers and sunscreen photostability, Cosmet. Toiletries, 2009, 124, 47–54.

    CAS  Google Scholar 

  8. E. Damiani, W. Baschong and L. Greci, UV-filter combinations under UV-A exposure: Concomitant quantification of over-all spectral stability and molecular integrity, J. Photochem. Photobiol., B, 2007, 87, 95–104.

    Article  CAS  Google Scholar 

  9. D. Dondi, A. Albini and N. Serpone, Interactions between different solar UVB/UVA filters contained in commercial suncreams and consequent loss of UV protection, Photochem. Photobiol. Sci., 2006, 5, 835–843.

    Article  CAS  Google Scholar 

  10. R. M. Sayre, J. C. Dowdy, A. J. Gerwig, W. J. Shields and R. V. Lloyd, Unexpected photolysis of the sunscreen octinoxate in the presence of the sunscreen avobenzone, Photochem. Photobiol., 2005, 81, 452–456.

    Article  CAS  Google Scholar 

  11. E. Chatelain and B. Gabard, Photostabilization of butyl methoxy-dibenzoylmethane (avobenzone) and ethylhexyl methoxycinnamate by bis-ethylhexyloxyphenol methoxyphenyl triazine (Tinosorb S), a new UV broadband filter, Photochem. Photobiol., 2001, 74, 401–406.

    Article  CAS  Google Scholar 

  12. A. Kikuchi and M. Yagi, Luminescence and electron paramagnetic resonance studies of the excited states of a UV absorber, 2-methylphenyl 2-naphthoate, Chem. Lett., 2009, 38, 770–771.

    Article  CAS  Google Scholar 

  13. A. Kikuchi, N. Oguchi and M. Yagi, Optical and electron paramagnetic resonance studies of the excited states of 4-tert-butyl-4’-methoxydibenzoylmethane and 4-tert-butyl-4’-methoxydibenzoyl-propane, J. Phys. Chem. A, 2009, 113, 13492–13497.

    Article  CAS  Google Scholar 

  14. A. Kikuchi, S. Yukimaru, N. Oguchi, K. Miyazawa and M. Yagi, Excited triplet state of a UV-B absorber, octyl methoxycinnamate, Chem. Lett., 2010, 39, 633–635.

    Article  CAS  Google Scholar 

  15. A. Kikuchi and M. Yagi, Direct observation of the intermolecular triplet–triplet energy transfer from UV-A absorber 4-tert-butyl-4’-methoxydibenzoylmethane to UV-B absorber octyl methoxycinnamate, Chem. Phys. Lett., 2011, 513, 63–66.

    Article  CAS  Google Scholar 

  16. N. J. Turro, V. Ramamurthy and J. C. Scaiano, Modern Molecular Photochemistry of Organic Molecules, Unversity Science Books, Sausalito, 2010.

    Google Scholar 

  17. M. Mori and H. Saito, Production of ultraviolet ray absorbing agent, Jpn. Tokkyo Koho, JP 4229979, 2009, Chem. Abstr., 2009, 150, 240425.

    Google Scholar 

  18. L. G. Thompson and S. E. Webber, The external heavy atom effect on the phosphorescence spectra of some halonaphthalenes, J. P hy s. Chem., 1972, 76, 221–224.

    Article  CAS  Google Scholar 

  19. S. P. McGlynn, T. Azumi and M. Kinoshita, Molecular Spec-troscopy of the Triplet State, Prentice-Hall, Engelwood Cliffs, 1969.

    Google Scholar 

  20. L. V. S. Hood and J. D. Winefordner, Use of external heavy atom effect to increase sensitivity of measurement in phosphorimetry, Anal. Chem., 1966, 38, 1922–1924.

    Article  CAS  Google Scholar 

  21. R. F. Bryan and D. P. Freyberg, Crystal structures of a-trans- and p-methoxy-cinnamic acids and their relation to thermal mesomorphism, J. Chem. Soc., Perkin Trans. 2, 1975, 1835–1840.

    Article  Google Scholar 

  22. L. E. Agrapidis-Paloympis, R. A. Nash and N. A. Shaath, The effect of solvent on the ultraviolet absorbance of sunscreens, J. Soc. Cosmet. Chem., 1987, 38, 209–221.

    CAS  Google Scholar 

  23. Z. R. Grabowski and A. Grabowska, The Förster cycle reconsidered, Z. Phys. Chem., 1976, 101, 197–208.

    Article  CAS  Google Scholar 

  24. M. Montalti, A. Credi, L. Prodi and M. T. Gandolfi, Handbook of photochemistry, Taylor & Francis, Boca Raton, 3rd edn, 2006.

    Book  Google Scholar 

  25. S. P. Huong, V. Andrieu, J.-P. Reynier, E. Rocher and J.-D. Fourneron, The photoisomerization of the sunscreen ethylhexyl p-methoxy cin-namate and its influence on the sun protection factor, J. Photochem. Photobiol., A, 2007, 186, 65–70.

    Article  CAS  Google Scholar 

  26. S. Pattanaargson, N. Hongchinnagorn, P. Hirunsupachot and Y. Sritana-anant, UV absorption and photoisomerization of p-methoxycinnamate grafted silicone, Photochem. Photobiol., 2004, 80, 322–325.

    Article  CAS  Google Scholar 

  27. S. Pattanaargson, T. Munhapol, P. Hirunsupachot and P. Luangth-ongaram, Photoisomerization of octyl methoxycinnamate anion, J. Photochem. Photobiol., A, 2004, 161, 269–274.

    Article  CAS  Google Scholar 

  28. Y. Shioya and M. Yagi, Time-resolved electron paramagnetic resonance study of the lowest excited triplet state of trans-cinnamic acid, J. Photochem. Photobiol., A, 1995, 86, 97–102.

    Article  CAS  Google Scholar 

  29. M. Yagi, I. Yamamoto, R. Sasase and K. Seki, Optical and time-resolved electron paramagnetic resonance studies of the excited states of para-methylcinnamic acid and para-methylcinnamate, Appl. Magn. Reson., 2003, 23, 421–434.

    Article  CAS  Google Scholar 

  30. P. Kottis and R. Lefebvre, Calculation of the electron spin resonance line shape of randomly oriented molecules in a triplet state. I. The, Dm = 2 transition with a constant linewidth, J. Chem. Phys., 1963, 39, 393–403.

    Article  CAS  Google Scholar 

  31. T. M. Karpkird, S. Wanichweacharungruang and B. Albinsson, Pho-tophysical characterization of cinnamates, Photochem. Photobiol. Sci., 2009, 8, 1455–1460.

    Article  CAS  Google Scholar 

  32. S. Niizuma, L. Kwan and N. Hirota, E.P.R. and zero-field odmr studies of the T1 states of halogen-containing benzonitriles, anisoles and anilines, Mol. Phys., 1978, 35, 1029–1046.

    Article  CAS  Google Scholar 

  33. G. Kothandaraman and D. S. Tinti, PMDR studies of intramolecular spin–orbit perturbations on the triplet state properties of substituted benzenes, Chem. Phys. Lett., 1973, 19, 225–230.

    Article  CAS  Google Scholar 

  34. S. A. Boorstein and M. Gouterman, Theory for zero-field splittings in aromatic hydrocarbons. III, J. Chem. Phys., 1963, 39, 2443–2452.

    Article  CAS  Google Scholar 

  35. W. T. Raynes, Spin splittings and rotational structure of nonlinear molecules in doublet and triplet electronic states, J. Chem. Phys., 1964, 41, 3020–3032.

    Article  CAS  Google Scholar 

  36. M. Deguchi, D. Suzuki, R. Ito, M. Matsumoto and M. Yagi, Time-resolved electron paramagnetic resonance of the lowest excited triplet state of phenazinium cation, Spectrochim. Acta, Part A, 2005, 61, 1147–1151.

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry, Graduate School of Engineering, Yokohama National University, Tokiwadai, Hodogaya-ku, Yokohama, 240-8501, Japan

    Azusa Kikuchi & Mikio Yagi

  2. Lead Chemical Company Ltd., Himata, Toyama, 930-0912, Japan

    Haruo Saito & Masao Mori

Authors
  1. Azusa Kikuchi
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Haruo Saito
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Masao Mori
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Mikio Yagi
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Azusa Kikuchi.

Additional information

CCDC reference number 828376. For crystallographic data in CIF or other electronic format see DOI: 10.1039/c1pp05168g

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Kikuchi, A., Saito, H., Mori, M. et al. Photoexcited triplet states of new UV absorbers, cinnamic acid 2-methylphenyl esters. Photochem Photobiol Sci 10, 1902–1909 (2011). https://doi.org/10.1039/c1pp05168g

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1039/c1pp05168g

Search

Navigation