Skip to main content
SpringerLink
Log in

Photophysics of 7-mercapto-4-methylcoumarin and derivatives: complementary fluorescence behaviour to 7-hydroxycoumarins

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

Abstract

The photophysical behaviour of 7-mercapto-4-methylcoumarin (C-SH) and derivatives has been studied in different solvents. In contrast to 7-hydroxy-4-methylcoumarin, C-SH shows poor emission, but high fluorescence when the thiol is alkylated. The origin and character of the lowest singlet states are discussed, specifically proposing that the thione-like C=S resonance form plays a key role in excited state deactivation in C-SH.

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. M. S. T. Gonçalves, Fluorescent Labeling of Biomolecules with Organic Probes, Chem. Rev., 2009, 109, 190–212.

    Article  Google Scholar 

  2. K. G. Reddie, W. H. Humphries, C. P. Bain, C. K. Payne, M. L. Kemp, and N. Murthy, Fluorescent Coumarin Thiols Measure Biological Redox Couples, Org. Lett., 2012, 14, 680–683. Y. Chen H. R. Liu H. S. Liu M. Cheng P. Xia K. D. Qian P. C. Wu C. Y. Lai Y. Xia Z. Y. Yang S. L. Morris-Natschke K. H. Lee, Antitumor agents 292. Design, synthesis and pharmacological study of S- and O-substituted 7-mercapto- or hydroxy-coumarins and chromones as potent cytotoxic agents, Eur. J. Med. Chem., 2012, 49, 74-85.

    Article  CAS  Google Scholar 

  3. W. Ji, N. Li, D. Chen, X. Qi, W. Sha, Y. Jiao, Q. Xu, and J. Lu, Coumarin-containing photo-responsive nanocomposites for NIR light-triggered controlled drug release via a two-photon process, J. Mater. Chem. B, 2013, 1, 5942–5949. P. Klan T. Solomek C. G. Bochet A. Blanc R. Givens M. Rubina V. Popik A. Kostikov J. Wirz, Photoremovable protecting groups in chemistry and biology: reaction mechanisms and efficacy, Chem. Rev., 2013, 113, 119-191.

    Article  CAS  Google Scholar 

  4. J. S. S. Demelo, R. S. Becker, and A. L. Macanita, Photophysical Behavior of Coumarins as a Function of Substitution and Solvent - Experimental-Evidence for the Existence of a Lowest Lying (1)(Eta,Pi(Asterisk)) State, J. Phys. Chem., 1994, 98, 6054–6058.

    Article  Google Scholar 

  5. J. R. Heldt, J. Heldt, M. Stori, and H. A. Diehl, Photophysical Properties of 4-Alkylcoumarin and 7-Alkoxycoumarin Derivatives - Absorption and Emission-Spectra, Fluorescence Quantum Yield and Decay Time, Spectrochim. Acta, Part A., 1995, 51, 1549–1563.

    Article  Google Scholar 

  6. D. Jacquemin, E. A. Perpete, G. Scalmani, M. J. Frisch, X. Assfeld, I. Ciofini, and C. Adamo, Time-dependent density functional theory investigation of the absorption, fluorescence, and phosphorescence spectra of solvated coumarins, J. Chem. Phys., 2006, 125, 164324.

    Article  Google Scholar 

  7. B. D. Wagner, The Use of Coumarins as Environmentally-Sensitive Fluorescent Probes of Heterogeneous Inclusion Systems, Molecules., 2009, 14, 210–237.

    Article  CAS  Google Scholar 

  8. C. L. Tung, H. Y. Lam, J. Xu, and X. Li, A fluorogenic probe for recognizing 5-hydroxylysine inspired by serine/threonine ligation, Chem. Commun., 2014, 50, 5298–5300. H. Woo Y. You T. Kim G.-J. Jhon W. Nam, Fluorescence ratiometric zinc sensors based on controlled energy transfer, J. Mater. Chem., 2012, 22, 17100-17112. E. González-García V. Helaine G. Klein M. Schuermann G. A. Sprenger W.-D. Fessner J.-L. Reymond, Fluorogenic Stereochemical Probes for Transaldolases, Chem.–Eur. J., 2003, 9, 893-899.

    Article  CAS  Google Scholar 

  9. G. I. N. Trendafilova, A. J. A. Aquino, and H. Lischka, Excited state properties off 7-hydroxy-4-methylcoumarin in the gas phase and in solution. A theoretical study, J. Phys. Chem. A, 2005, 109, 11860–11869. N. Nizomov A. U. Kholov A. A. Ishchenko V. V. Ishchenko V. P. Khilya, Electronic structure and spectral fluorescence properties of umbelliferone and herniarin, J. Appl. Spectrosc., 2007, 74, 626-634. J. Donovalova M. Cigan H. Stankovicova J. Gaspar M. Danko A. Gaplovsky P. Hrdlovic, Spectral Properties of Substituted Coumarins in Solution and Polymer Matrices, Molecules, 2012, 17, 3259-3276. C. M. Krauter J. Mohring T. Buckup M. Pernpointner M. Motzkus, Ultrafast branching in the excited state of coumarin and umbelliferone, Phys. Chem. Chem. Phys., 2013, 15, 17846-17861. T. Sakurai H. Mizoguchi S. Yamada H. Inoue, Proton-transfer reactions between 7-hydroxycoumarin and tertiary amines. Formation of the ground-state tautomer anion, Ber. Bunsenges. Phys. Chem., 1996, 100, 505-507. W. R. Sherman E. Robins, Fluorescence of Substituted 7-Hydroxycoumarins, Anal. Chem., 1968, 40, 803-805.

    Article  Google Scholar 

  10. J. S. de Melo, and P. F. Fernandes, Spectroscopy and photophysics of 4-and 7-hydroxycoumarins and their thione analogs, J. Mol. Struct., 2001, 565, 69–78.

    Article  Google Scholar 

  11. M. Gonzalez-Bejar, M. Frenette, L. Jorge, and J. C. Scaiano, 7-Mercapto-4-methylcoumarin as a reporter of thiol binding to the CdSe quantum dot surface, Chem. Commun., 2009, 22, 3202–3204. M. Dübner T. N. Gevrek A. Sanyal N. D. Spencer C. Padeste, Fabrication of Thiol–Ene “Clickable” Copolymer-Brush Nanostructures on Polymeric Substrates via Extreme Ultraviolet Interference Lithography, ACS Appl. Mater. Interfaces., 2015, 7, 11337-11345.

    Article  Google Scholar 

  12. S. G. Schulman, and L. S. Rosenberg, Tautomerization Kinetics of 7-Hydroxy-4-Methylcoumarin in the Lowest Excited Singlet-State, J. Phys. Chem., 1979, 83, 447–451.

    Article  CAS  Google Scholar 

  13. N. J. R. Turro, V. Ramamurthy, and J. C. Scaiano, Modern Molecular Photochemistry of Organic Molecules, University Science Publishers, New York, N.Y., 2010.

    Google Scholar 

  14. J. S. deMelo, R. S. Becker, F. Elisei, and A. L. Macanita, The photophysical behavior of 3-chloro-7-methoxy-4-methylcoumarin related to the energy separation of the two lowest-lying singlet excited states, J. Chem. Phys., 1997, 107, 6062–6069.

    Article  Google Scholar 

  15. L. Cisse, A. Djande, M. Capo-Chichi, F. Delatre, A. Saba, A. Tine, and J.-J. Aaron, Revisiting the photophysical properties and excited singlet-state dipole moments of several coumarin derivatives, Spectrochim. Acta, Part A., 2011, 79, 428–436.

    Article  CAS  Google Scholar 

  16. Y. Liu, J. Ding, R. Liu, D. Shi, and J. Sun, Revisiting the electronic excited-state hydrogen bonding dynamics of coumarin chromophore in alcohols: Undoubtedly strengthened not cleaved, J. Photochem. Photobiol., A, 2009, 201, 203–207. G.-J. Zhao K.-L. Han, Hydrogen Bonding in the Electronic Excited State, Acc. Chem. Res., 2012, 45, 404-413.

    Article  CAS  Google Scholar 

  17. B. Valeur, and M. N. Berberan-Santos, in Molecular Fluorescence, Wiley-VCH Verlag GmbH & Co. KGaA, 2012, pp. 109–140.

    Book  Google Scholar 

  18. G.-J. Zhao, and K.-L. Han, Early Time Hydrogen-Bonding Dynamics of Photoexcited Coumarin 102 in Hydrogen-Donating Solvents: Theoretical Study, J. Phys. Chem. A., 2007, 111, 2469–2474.

    Article  CAS  Google Scholar 

  19. X. Liu, J. M. Cole, P. G. Waddell, T. C. Lin, J. Radia, and A. Zeidler, Molecular origins of optoelectronic properties in coumarin dyes: toward designer solar cell and laser applications, J. Phys. Chem. A, 2012, 116, 727–737. A. P. Demchenko, Advanced fluorescence reporters in chemistry and biology I fundamentals and molecular design, Springer, Berlin, Germany, 2010., M. Frenette C. Coenhart J. C. Scaiano, Mapping Acid-Catalyzed Deprotection in Thin Polymer Films: Fluorescence Imaging Using Prefluorescent 7-Hydroxycoumarin Probes, Macromol. Rapid Commun., 2004, 25, 1628-1631. Z. Wu Z. Li L. Yang J. Hanb S. Han, Fluorogenic detection of hydrogen sulfide via reductive unmasking of o-azidomethylbenzoyl-coumarin conjugate, Chem. Commun., 2012, 48, 10120-10122.

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The Natural Sciences and Engineering Research Council of Canada supported this work through its Discovery and graduate scholarships programs. Thanks are due to the Canada Research Chairs program for an award to J. C. S. and to summer student Phillip Campbell for his help with some measurements.

Author information

Authors and Affiliations

  1. Center of Catalysis Research and Innovation (CCRI) and Department of Chemistry and Biomolecular Sciences, University of Ottawa, Canada

    Anabel E. Lanterna, María González-Béjar, Mathieu Frenette & Juan C. Scaiano

  2. Instituto de Ciencia Molecular (ICMol)/Departamento de, Química Orgánica, Universidad de Valencia, C/Catedrático José Beltrán 2, 46980, Paterna, Valencia, Spain

    María González-Béjar

  3. Département de Chimie, Université du Québec À Montréal, Montreal, QC, Canada

    Mathieu Frenette

Authors
  1. Anabel E. Lanterna
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. María González-Béjar
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Mathieu Frenette
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Juan C. Scaiano
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Juan C. Scaiano.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Lanterna, A.E., González-Béjar, M., Frenette, M. et al. Photophysics of 7-mercapto-4-methylcoumarin and derivatives: complementary fluorescence behaviour to 7-hydroxycoumarins. Photochem Photobiol Sci 16, 1284–1289 (2017). https://doi.org/10.1039/c7pp00121e

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1039/c7pp00121e

Search

Navigation