Dielectric, Photophysical, Solvatochromic, and DFT Studies on Laser Dye Coumarin 334

  • C. V. Maridevarmath
  • Lohit Naik
  • G. H. MalimathEmail author
Atomic Physics


The absorption and fluorescence spectra of laser dye, 10-acetyl-2,3,6,7-tetrahydro-1H,5H,11H-pyrano[2,3-f]pyrido[3,2,1-ij]quinolin-11-one [C-334], are recorded. The ground-state dipole moments (μg) were determined from density functional theory (DFT) computations, Guggenheim’s, and solvatochromic methods. The excited-state dipole moments (μe) were determined from Lippert’s, Bakhshiev’s, Kawski-Chamma-Viallet’s, and McRae’s equations. The μe values are found to be higher than μg values and this suggest that the probe molecule is more polar in the excited state. The absorption maxima and emission maxima of C-334 undergo bathochromic shift as the polarity of the solvent increases and indicates that the transitions involved are π → π*. The change in dipole moment (Δμ) and the angle between μe and μg is calculated. The absorption and fluorescence emission of the probe C-334 were investigated theoretically with the help of Gaussian 09W for all the studied solvents by using time-dependent (TD)-DFT combined with conductor-like polarizable continuum model (CPCM) solvation model and were compared with the experimental results. Further, the ground- and excited-state dipole moments were also estimated for all the studied solvents by using CPCM solvation model and are compared with the experimental results. The HOMO-LUMO energy gaps computed using DFT and from absorption threshold wavelengths are found to be in order with each other. The chemical hardness (η) of the probe molecule is estimated and the results suggest the soft nature of the molecule. Further, the reactive centers like electrophilic site and nucleophilic site were identified with the help of molecular electrostatic potential (MESP) 3D plots using DFT computational analysis.


Coumarin 334 Guggenheim’s method Solvatochromic DFT HOMO-LUMO 



The authors are thankful to the authorities of USIC, KUD, for providing the instrumental facility for our research work. One of the authors (CVM) is thankful to the Principal Prof. B.P. Urakadli and staff, Government First Grade College Hubballi, for their continuous support and encouragement.


  1. 1.
    N.K. Hamdi, M.M. Chebli, H. Grib, M. Brahimi, A.M.S. Silva, Synthesis DFT/TD-DFT theoretical studies and experimental solvatochromic shift methods on determination of ground and excited state dipole moments of 3-(2-hydroxybenzoyl) coumarins. Journal of Molecular Structure 1175, 811–820 (2019)ADSCrossRefGoogle Scholar
  2. 2.
    N. Khanapurmath, M.V. Kulkarni, L. Pallavi, J. Yenagi, J. Tonannavar, Solvatochromic studies on 4-bromomethyl-7-methyl coumarins. Journal of Molecular Structure 1160, 50–56 (2018)ADSCrossRefGoogle Scholar
  3. 3.
    S. Samundeeswari, M.V. Kulkarni, J. Yenagi, J. Tonannavar, Dual fluorescence and solvatochromic study on 3-acyl coumarins. J. Fluoresc. 27, 1247–1255 (2017). CrossRefGoogle Scholar
  4. 4.
    J. Basavaraj, H.M. Sureshkumar, S.R. Inamdar, M.N. Wari, Estimation of ground and excited state dipole moment of laser dyes C504T and C521T using solvatochromic shifts of absorption and fluorescence spectra. Spectrochim. Acta Part A-Molecular and Biomolecular Spectro 154, 177 (2016)Google Scholar
  5. 5.
    U.S. Raikar, V.B. Tangod, S.R. Mannopantar, B.M. Mastiholli, Ground and excited state dipole moments of coumarin 337 laser dye. Optics Communication 283, 4289–4292 (2010)ADSCrossRefGoogle Scholar
  6. 6.
    J. Basavaraj, S.R. Inamdar, H.M. Sureshkumar, Solvent effects on the absorption and fluorescence spectra of 7-diethylamino-3-thienoylcoumarin: Evaluation and correlation between solvatochromism and solvent polarity parameters. Spectrochim. Acta Part A-Molecular and Biomolecular Spectro 137, 527 (2015)Google Scholar
  7. 7.
    E.J. Schitschek, J.A. Trias, P.R. Hammond, R.A. Henry, R.L. Atkins, New laser dyes with blue-green emission. Optics Communication 16, 313–316 (1976)ADSCrossRefGoogle Scholar
  8. 8.
    C. Parkanyi, M.S. Antonious, J.J. Aaron, M. Buna, A. Tine, L. Cissa, Determination of the first excited singlet state dipole moments of coumarins by the solvatochromic method. Spectro. Letters 27, 439–449 (1994)ADSCrossRefGoogle Scholar
  9. 9.
    E. Perez-Rodriguez, J. Aguilera, F.L. Figueroa, J. Expt, Tissular localization of coumarins in the green alga Dasycladus vermicularis (Scopoli) Krasser: a photoprotective role? Botany 54, 1093 (2003)Google Scholar
  10. 10.
    K.H. Drexhage, Structure and properties of laser dyes, (Springer-Verlag, Berlin, 1973)Google Scholar
  11. 11.
    J. Thipperudrappa, D.S. Biradar, S.R. Manohara, S.M. Hanagodimath, S.R. Inamadar, R.J. Manekutla, Solvent effects on the absorption and fluorescence spectra of some laser dyes: Estimation of ground and excited-state dipole moments. Spectrochim. Acta Part A- Molecular and Biomolecular Spectro 69, 991–997 (2008)Google Scholar
  12. 12.
    W.R. Shermon, E. Robins, Fluorescence of substituted 7-hydroxycoumarins. Anal. Chem. 40, 803–805 (1968)CrossRefGoogle Scholar
  13. 13.
    A. Evangelos, P.D. Andrew, Convenient microscale synthesis of a coumarin laser dye analog. Journal of Chemical Education 83(2), 287 (2006)Google Scholar
  14. 14.
    A. Lacy, R. Kennedy, Studies on coumarins and coumarin-related compounds to determine their therapeutic role in the treatment of cancer. Current Pharmaceutical Design 10, 3797–3811 (2004)CrossRefGoogle Scholar
  15. 15.
    V.U. Jeankumar, R.S. Reshma, R. Janupally, S. Saxena, J.P. Sridevi, B. Medapi, P. Kulkarni, P. Yogeeswari, D. Sriram, Enabling the (3 + 2) cycloaddition reaction in assembling newer anti-tubercular lead acting through the inhibition of the gyrase ATPase domain: lead optimization and structure activity profiling. Organic & Biomolecular Chemistry 13, 2423–2431 (2015)CrossRefGoogle Scholar
  16. 16.
    D. Yu, M. Suzuki, L. Xie, S.L. Morris-Natschke, K.H. Lee, Recent progress in the development of coumarin derivatives as potent anti-HIV agents. Med. Res. Rev. 23, 322–345 (2003)CrossRefGoogle Scholar
  17. 17.
    R.D. Thornes, D.W. Edlow, S. Wood, Inhibition of locomotion of cancer cells in vivo by anticoagulant therapy. I. Effects of sodium warfarin on V2 cancer cells, granulocytes, lymphocytes and macrophages in rabbits. The Johns Hopkins Medical Journal 123, 305 (1968)Google Scholar
  18. 18.
    D.Z. N’u˜nez, P. Barrias, G.C. Jir’on, M.S.U. Za˜nartu, C.L. Alarc’on, F.E.M. Vieyra, C.D. Borsarelli, E.I. Alarcon, A. Asp’ee, A typical antioxidant activity of non-phenolic amino-coumarins. RSC Advances 8, 1927 (2018)Google Scholar
  19. 19.
    M. Vaculovicova, S. Dostalova, V. Milosavljevic, P. Kopel, V. Adam, R. Kizek, Characterization of carbon quantum dots by capillary electrophoresis with laser-induced fluorescence detections. J. Metallomics & Nanotechno. 3, 97 (2015)Google Scholar
  20. 20.
    R. Konecna, H. Viet Nguyen, M. Stanisavljevic, I. Blazkova, S. Krizkova, M. Vaculovicova, M. Stiborova, T. Eckschlager, O. Zitka, V. Adam, R. Kizek, Doxorubicin encapsulation investigated by capillary electrophoresis with laser-induced fluorescence detection. Chromatographia 77, 1469–1476 (2014)CrossRefGoogle Scholar
  21. 21.
    M.H. Kim, H.H. Jang, S. Yi, S.K. Chang, M.S. Han, Coumarin-derivative-based off–on catalytic chemodosimeter for Cu2+ ions. Chemical Communications 4838 (2009)Google Scholar
  22. 22.
    J. Huang, V. Bekiari, P. Lianos, S. Couris, Study of poly(methyl methacrylate) thin films doped with laser dyes. J. Luminescence 81, 285–291 (1999)ADSCrossRefGoogle Scholar
  23. 23.
    C. Reichardt, Solvents and Solvent Effects in Organic Chemistry, 3rd edn. (Wiley-VCH, New York, 2004)Google Scholar
  24. 24.
    U.P. Raghavendra, M. Basanagouda, R.M. Melavanki, R.H. Fattepur, J. Thipperudrappa, Solvatochromic studies of biologically active iodinated 4-aryloxymethyl coumarins and estimation of dipole moments. J. Mol. Liq. 202, 9–16 (2015)CrossRefGoogle Scholar
  25. 25.
    S.S. Patil, G.V. Muddapur, N.R. Patil, R.M. Melavanki, R.A. Kusanur, Fluorescence characteristics of aryl boronic acid derivative (PBA). Spectrochim. Acta Part A- Molecular and Biomolecular Spectro 138, 85–91 (2015)Google Scholar
  26. 26.
    S.K. Patil, M.N. Wari, P.C. Yohannan, S.R. Inamdar, Determination of ground and excited state dipole moments of dipolar laser dyes by solvatochromic shift method. Spectrochim. Acta Part A- Molecular and Biomolecular Spectro 123, 117–126 (2014)Google Scholar
  27. 27.
    G.V. Muddapur, N.R. Patil, S.S. Patil, R.M. Melavanki, R.A. Kusanur, Estimation of ground and excited state dipole moments of aryl boronic acid derivative by solvatochromic shift method. J. Fluoresc. 24, 1651–1659 (2014)CrossRefGoogle Scholar
  28. 28.
    J.S. Kadadevarmath, G.H. Malimath, N.R. Patil, H.S. Geetanjali, R.M. Melavanki, Solvent effect on the dipole moments and photo physical behaviour of 2,5-di-(5-tert-butyl-2-benzoxazolyl) thiophene dye. Canadian Journal of Physiology and Pharmacology 91, 1107–1113 (2013)ADSCrossRefGoogle Scholar
  29. 29.
    J.R. Manekutla, B.G. Mulimani, S.R. Inamdar, Solvent effect on absorption and fluorescence spectra of coumarin laser dyes: Evaluation of ground and excited state dipole moments. Spectrochim. Acta Part A- Molecular and Biomolecular Spectro 69, 419 (2008)Google Scholar
  30. 30.
    D.S. Biradar, B. Siddlingeshwar, S.M. Hanagodimath, Estimation of ground and excited state dipole moments of some laser dyes. J. Mol. Struct. 875, 108–112 (2008)ADSCrossRefGoogle Scholar
  31. 31.
    J. Czekella, Two electro optical methods for determination of dipole moments of excited molecules. Chimia 15, 26 (1961)Google Scholar
  32. 32.
    J. Czekella, Elektrische Fluoreszenzpolarisation: Die Bestimmung von Dipolmomenten angeregter Moleküle aus dem Polarisationsgrad der Fluoreszenz in starken elektrischen Feldern. Z. Elaktrochem. 64, 1221 (1960)Google Scholar
  33. 33.
    M.P. Hass, J.M. Warman, Photon-induced molecular charge separation studied by nanosecond time-resolved microwave conductivity. Chemistry and Physics of Lipids 73, 35–53 (1982)Google Scholar
  34. 34.
    J.R. Lombardi, Correlation between structure and dipole moments in the excited states of substituted benzenes. Journal of the American Chemical Society 92, 1831–1833 (1970)CrossRefGoogle Scholar
  35. 35.
    E.A. Guggenheim, The computation of electric dipole moments. Transactions of the Faraday Society 47, 573 (1951)CrossRefGoogle Scholar
  36. 36.
    L. Naik, N. Deshapande, I.A.M. Khazi, G.H. Malimath, Resonance energy transfer studies from derivatives of thiophene substituted 1,3,4-oxadiazoles to coumarin-334 dye in liquid and dye-doped polymer media. Brazilian Journal of Physics 48, 16–24 (2017). ADSCrossRefGoogle Scholar
  37. 37.
    E.Z. Lippert, Spektroskopische Bestimmung des Dipolmomentes aromatischer Verbindungen im ersten angeregten Singulettzustand. Zeitschrift für Elektrochemie 61, 962 (1957)Google Scholar
  38. 38.
    N.G. Bakhshiev, Universal intermolecular interactions and their effect on the position of the electronic spectra of molecules in 2-component solutions. Optika i Spektroskopiya 16(5), 821 (1964)Google Scholar
  39. 39.
    A. Kawski, On the estimation of excited state dipole moments from solvatochromic shifts of absorption and fluorescence spectra. Zeitschrift für Naturforschung 57A, 255 (2002)Google Scholar
  40. 40.
    U.S. Raikar, V.B. Tangod, B.M. Mastiholli, S. Sreenivasa, Solvent effects and photophysical studies of ADS560EI laser dye. African Journal of Pure and Applied Chemistry 4(9), 188 (2010)Google Scholar
  41. 41.
    K.B. Akshaya, V. Anitha, L.L. Prajwal, K. Rekakumari, G. Louis, Synthesis and photophysical properties of a novel phthalimide derivative using solvatochromic shift method for the estimation of ground and singlet excited state dipole moments. Journal of Molecular Liquids 224, 247–254 (2016)CrossRefGoogle Scholar
  42. 42.
    A. Roshmy, V. Anita, G. Louis, N. Aatika, Estimation of ground state and excited state dipole moments of a novel Schiff base derivative containing 1,2,4-triazole nucleus by solvatochromic method. J. Mol. Liq. 215, 387 (2016)Google Scholar
  43. 43.
    S.R. Manohara, V.U. Kumar, G.L. Shivakumaraiah, Estimation of ground and excited-state dipole moments of 1, 2-diazines by solvatochromic method and quantum-chemical calculation. J. Mol. Liq. 181, 97–104 (2013)CrossRefGoogle Scholar
  44. 44.
    R.G. Pearson, Chemical Hardness (Wiley - VCH, Weinheim, 1997)CrossRefGoogle Scholar

Copyright information

© Sociedade Brasileira de Física 2019

Authors and Affiliations

  • C. V. Maridevarmath
    • 1
  • Lohit Naik
    • 2
  • G. H. Malimath
    • 2
    Email author
  1. 1.Department of PhysicsGovernment First Grade CollegeHubballiIndia
  2. 2.UG and PG Department of PhysicsKarnataka Science CollegeDharwadIndia

Personalised recommendations