Skip to main content
SpringerLink
Log in

Solvent Dependence on Structure and Electronic Properties of 7-(Diethylamino) - 2H -1- Benzopyran-2- one (C-466) Laser Dye

  • ORIGINAL ARTICLE
  • Published:
Journal of Fluorescence Aims and scope Submit manuscript

Abstract

In this work, we studied influences on the absorption and fluorescence emission spectra of coumarin-4066 (C-466) with different solvent polarity scale. The spectral shifts reflect the effect of the equilibrium solvents association across the energized solute particle, which adjusts inertially as a result of quick charge realignment upon radiative deactivation to the lowest electronic state. The dipole moments of C-466 are determined by employing the Bakhshiev, Kawski-Chamma-Viallet, Lippert-Mataga and McRae relations. The results from all these methods are, excited state dipole moment of C-466 is higher than the ground state dipole moments and which indicates molecule is less polar in the ground state. Theoretical analysis was also carried out by Density Functional theory (DFT and TD –DFT) employing the BECKE-1998 (exchange)/STO-6G basic set in ethanol solvent and in vacuum medium. The HOMO-LUMO, Solvent Accessible Surfaces (SAS) and Molecular Electrostatic Potential (MEP) were analysed to acquire additional knowledge of the molecular arrangement and electronic properties of C-466. These photophysical properties suggest delineation can be mauled for laying out new luminescent tests for various solvents microenvironment.

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

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11
Fig. 12
Fig. 13
Fig. 14
Fig. 15
Fig. 16
Fig. 17

Similar content being viewed by others

References

  1. Bouckaert C, Serra S, Rondelet G, Dolusic E, Wouters J, Dogne JM, Frederick R, Pochet L (2016) Synthesis, evaluation and structure–activity relationship of new 3-carboxamide coumarins as FXIIa inhibitors. Eur J Med Chem 110:181–194

    Article  PubMed  CAS  Google Scholar 

  2. Sidarai AH, Desai VR, Hunagund SM, Basanagouda M, Kadadevarmath JS (2017) Study of Photophysical properties on newly synthesized Coumarin derivatives. J Fluoresc 27:2223–2229

    Article  PubMed  CAS  Google Scholar 

  3. Al-Kawkabani A, Makhloufi-Chebli M, Benosmane N, Boutemeur-Kheddis B, Hamdi M, Silva AMS (2017) Study of the novel fluorescent 4-methyl-9-(3-oxobutanoyl)-2H,8H-pyrano[2,3-f]chromene-2,8-dione derivative. Estimation of the ground- and excited-state dipole moments from a solvatochromic shift. J Mol Struct 1146:285–229

    Article  CAS  Google Scholar 

  4. Kumari R, Varghese A, George L (2017) Estimation of ground-state and singlet excited-state dipole moments of substituted schiff bases containing oxazolidin-2-one moiety through solvatochromic methods. J Fluoresc 27:151–165

    Article  PubMed  CAS  Google Scholar 

  5. Renuka CG, Shivashankar K, Boregowda P, Bellad SS, Muregendrappa MV, Nadaf YF (2017) An experimental and computational study of 2-(3-Oxo- 3H-benzo[f] chromen-1- ylmethoxy)-benzoic acid methyl ester. J Sol Chem 46(8):1–22

    Article  CAS  Google Scholar 

  6. Joshi S, Kumari S, Sarmah A, Sakhuja R, Debi D (2016) Pant, Solvatochromic shift and estimation of dipole moment of synthesized coumarin derivative: Application as sensor for fluorogenic recognition of Fe3 + and Cu2 + ions in aqueous solution. J Mol Liq 222:253–262

    Article  CAS  Google Scholar 

  7. Durairaj A, Obadiah A, Ramanathan S, Johnson PM, Bella AP, Vasanthkumar S (2017) Synthesis, Characterization and Solvatochromic Studies Using the Solvent Polarity Parameter, ENT on 2-Chloro-3-Ethylamino-1,4-Naphthoquinone. 27:1505–1512

  8. Benjamin LC, Dannielle GM, Rodrigo N, Samuel BP, Milan D, David DD, Sukrit M, Timothy SD, Naomi SG (2017) Tuning thermally activated delayed fluorescence emitter Photophysics through solvation in the solid state. ACS Energy Lett 2:1526–1533

    Article  CAS  Google Scholar 

  9. Ghazy R, Azim SA, Shaheen M, El-Mekawey F (2004) Experimental studies on the determination of the dipole moments of some different laser dyes. Spectrochim Acta Part A Mol Biomol Spectrosc 60(1–2):187–191

    Article  CAS  Google Scholar 

  10. Farley CM, Dibwe DF, Ueda JY, Hall EA, Awale S, Magolan J (2016) Evaluation of synthetic coumarins for antiausterity cytotoxicity against pancreatic cancers. Med Chem Lett 26:1471–1474

    Article  CAS  Google Scholar 

  11. Gasbarri C, Angelini G (2017) Polarizability over dipolarity for the spectroscopic behavior of azobenzenes in room-temperature ionic liquids and organic solvents. J Mol Liq 229:185–188

    Article  CAS  Google Scholar 

  12. Bhattacharya B, Samanta A (2007) Laser flash photolysis study of the aminophthalimide derivatives: elucidation of the nonradiative deactivation route. Chem Phys Lett 442(4–6):316–321

    Article  CAS  Google Scholar 

  13. Reichardt C, Welton T (2010) Solvents and solvent effects in Org Chem Wiley-VCH Verlag GmbH and Co, Weinheim

  14. Lakowicz JR (2006) Principles of fluorescence spectroscopy, Third edn. Plenum, New York

  15. Stevens TS (1957) Chemistry of carbon compounds, IV A. Elsevier, Ed, By E.M. Rodd, Amsterdam

  16. Lippert E (1957) Spektroskopische bistimmung des dipolmomentes aromatischer verbindugen im ersten angeregten singulettzustand. Z Electrochem 61:962–975

    CAS  Google Scholar 

  17. Bakshiev NG (1964) Universal intermolecular interactions and their effect on the position of the electronic spectra of molecules in two component solutions. Opt Specrtrosc 16:821–832

    Google Scholar 

  18. Chamma A, Viallet P (1970) Determination du moment dipolaire d’une molecule dans un etat excite singulet. Sci Paris Ser C 270:1901–1904

    CAS  Google Scholar 

  19. McRae EG (1957) Theory of solvent effects on molecular electronic spectra frequency shifts. J Phys Chem 61:562–572

    Article  CAS  Google Scholar 

  20. Edward JT (1956) Molecular volumes and parachor. Chem Ind 30:774–777

    Google Scholar 

  21. Reichardt C (2005) Solvents and solvent effects in organic chemistry, VCH, Weinhwim;1988. Solvents and solvent effects in organic chemistry, VCH. In: New York

    Google Scholar 

  22. Kamlet MJ, Abboud JLM, Abraham MH, Taft RW (1983) Linear solvation energy relationships. A comprehensive collection of the solvatochromic parameters, π*, α, and β, and some methods for simplifying the generalized solvatochromic equation. J Org Chem 48:2877–2887

    Article  CAS  Google Scholar 

  23. Kamlet MJ, Abboud JLM, Taft RW (1977) The solvatochromic comparison method. 6. The π* scale of solvent polarities. J Am Chem Soc 99:6027–6035

    Article  CAS  Google Scholar 

  24. Pramanik S, Banerjee P, Sarkar A, Mukherjee A, Mahalanabis KK, Bhattacharya SC. Spectroscopic investigation of 3-pyrazolyl 2-pyrazoline derivative in homogeneous solvents. Spectrochim Acta Part A Mol Biomol Spectrosc 2008; 71:1327–1332

  25. Homocianu M, Airinei A, Dorohoi DO (2011) Solvent effects on the electronic absorption and fluorescence spectra. J Adv Res 2:1–9

    Article  Google Scholar 

  26. Sidir I, Gulseven Sidir Y, Kumalar M, Tasal E (2010) Ab initio Hartree-Fock and density functional theory investigations on the conformational stability, molecular structure and vibrational spectra of 7-acetoxy-6-(2,3-dibromopropyl)-4,8-dimethylcoumarin molecule. J Mol Struct 964:134–151

    Article  CAS  Google Scholar 

  27. Sidir I, Sidir YG. Solvent effect on the absorption and fluorescence spectra of 7-acetoxy-6-(2,3-dibromopropyl)-4,8-dimethylcoumarin: determination of ground and excited state dipole moments. Spectrochim Acta Part A Mol Biomol Spectrosc 2013; 102: 286–296

  28. Nadaf YF, Mulimani BG, Inamdar SR (2004) Ground and excited state dipole moments of some exalite UV laser dyes from solvatochromic method using solvent polarity parameters. J Mol Struct THEOCHEM 678:177–181

    Article  CAS  Google Scholar 

  29. Raikar US, Renuka CG, Nadaf YF, Mulimani BG, Karguppikar AM, Soudagar MK. Solvent effects on the absorption and fluorescence spectra of coumarins 6 and 7 molecules: determination of ground and excited state dipole moment. Spectrochim Acta Part A Mol Biomol Spectrosc 2006; 65: 673–677

  30. Masoud MS, Hagagg SS, Ali AE, Nasr NM (2012) Solvatochromic behaviour of the electronic absorption spectra of gallic acid and some of its azo derivatives. Spectrochim Acta Part A Mol Biomol Spectrosc 94:256–264

    Article  CAS  Google Scholar 

  31. Singh M, Singh AK, Kumar R (2017) Investigation of charge-separation/change in dipole moment of 7-azaindole: quantitative measurement using solvatochromic shifts and computational approaches. J Mol Liq 231:39–44

    Article  CAS  Google Scholar 

  32. Avadanei M, Cozan V, Avadanei O (2017) Solvatochromic properties of two related N -salicylidenanilines with dual fluorescence. J Mol Liq 227:76–86

    Article  CAS  Google Scholar 

  33. Panigrahi M, Patel S, Mishra BK (2013) Solvatochromism of some hemicyanines. J Mol Liq 177:335–342

    Article  CAS  Google Scholar 

  34. Kamlet MJ, Taft RW (1976) The solvatochromic comparison method. The α-scale of solvent hydrogen-bond donor (HBD) acidities. J Am Chem Soc 98:377–383

    Article  CAS  Google Scholar 

  35. Schmidt MW, Baldridge KK, Boatz JA, Elbert ST, Gordon MS, Jensen JH, Koseki S, Matsunaga N, Nguyen KA, Su S, Windus TL, Dupuis M, Montgomery JA (1993) General atomic and molecular electronic structure system. J Comput Chem 14:1347–1363

    Article  CAS  Google Scholar 

  36. Suvitha A, Periandy S, Gayathri P (2015) NBO, HOMO–LUMO, UV, NLO, NMR and vibrational analysis of veratrole using FT-IR, FT-Raman, FT-NMR spectra and HF–DFT computational methods. Spectrochim Acta Part A Mol Biomol Spectrosc 138:357–369

    Article  CAS  Google Scholar 

  37. Chand S, Al-omary FAM, El-emam AA, Shukla VK, Prasad O, Sinha L (2015) Study on molecular structure, spectroscopic behavior, NBO, and NLO analysis of 3-methylbezothiazole-2-thione. Spectrochim Acta Part A Mol Biomol Spectrosc 146:129–141

    Article  CAS  Google Scholar 

  38. Soliman SM, Hagar M, Ibid F, Sayed E, El Ashry H (2015) Experimental and theoretical spectroscopic studies, HOMO–LUMO, NBO analyses and thione – thiol tautomerism of a new hybrid of 1, 3, 4-oxadiazole-thione with quinazolin-4-one. Spectrochim Acta Part A Mol Biomol Spectrosc 145:270–279

    Article  CAS  Google Scholar 

  39. Soliman SM, Albering J, Abu-youssef MAM (2015) Molecular structure, spectroscopic properties, NLO, HOMO–LUMO and NBO analyses of 6-hydroxy-3 (2H) –pyridazinone. Spectrochim Acta Part A Mol Biomol Spectrosc 136:1086–1098

    Article  CAS  Google Scholar 

  40. Balachandran V, Lalitha S, Rajeswari S (2012) Density functional theory, comparative vibrational spectroscopic studies, NBO, HOMO–LUMO analyses and thermodynamic functions of N- (bromomethyl) phthalimide and N- (chloromethyl) phthalimide. Spectrochim Acta Part A Mol Biomol Spectrosc 91:146–157

    Article  CAS  Google Scholar 

  41. Anton Georgiev, Anton Kostadinov, Deyan Ivanov, Deyan Dimov, Simeon Stoyanov Lian Nedelchev, Dimana Nazarova, Denitsa Yancheva. Synthesis, spectroscopic and TD-DFT quantum mechanical study of azo-azomethine dyes. A laser induced trans-cis-trans photoisomerization cycle. Spectrochim Acta Part A Mol Biomol Spectrosc 2018; 192:263–274

  42. Toy M, Tanak H (2016) Molecular structure and vibrational and chemical shift assignments of 3 0-chloro-4-dimethylamino azobenzene by DFT calculations. Spectrochim Acta Part A Mol Biomol Spectrosc 152:530–536

    Article  CAS  Google Scholar 

  43. Isa Sidir, Yadigar Gulseven Sidir. Solvatochromism and intramolecular hydrogen-bonding assisted dipole moment of phenyl 1-hydroxy-2-naphthoate in the ground and excited states. J Mol Liq 2016;221:972–985

  44. Asiri AM, Sobahi TR, Osman OI, Khan SA (2017) Photophysical investigation of (D- p -a) DMHP dye : dipole moments, photochemical quantum yield and fluorescence quantum yield, by solvatochromic shift methods and DFT studies. J Mol Struct 1128:636–644

    Article  CAS  Google Scholar 

  45. Sanmillan JL, Fernandez-Coello A, Fernandez-Conejero I, Plans G, Gabarros A (2017) Functional approach using intraoperative brain mapping and neurophysiological monitoring for the surgical treatment of brain metastases in the central region. J Neurosurg 126:698–707

    Article  PubMed  Google Scholar 

  46. Thirumala PD, Crammond DJ, Loke YK, Cheng HL, Huang J, Balzer JR (2017) Diagnostic accuracy of motor evoked potentials to detect neurological deficit during idiopathic scoliosis correction: a systematic review. J Neurosurg Spine 26:374–383

    Article  PubMed  Google Scholar 

  47. Gowda V, Laitinen RS, Telkki VV, Larsson AC, Antzutkin ON, Lantto P (2016) DFT calculations in the assignment of solid-state NMR and crystal structure elucidation of a lanthanum(III) complex with dithiocarbamate and phenanthroline. Dalton Trans 45:19473–19484

    Article  PubMed  CAS  Google Scholar 

  48. Penghui Ren, Yuehua Zhang, Zhiwen Luo, Peng Song, Yuanzuo Li. Theoretical and experimental study on spectra, electronic structure and photoelectric properties of three nature dyes used for solar cells. J Mol Liq 2017; 247:193–206

  49. Ayyanar Karuppasamy, Chandran Udhaya kumar, Muthiah Pillai Velayutham Pillai, Chennan Ramalingan. Synthesis, spectral, structural and DFT studies of novel dialkylfluorene decorated phenothiazine-3-carbaldehyde. J Mol Struct 2017; 1133:154–162

  50. Isa Sıdır, Yadigar Gulseven Sidir, Halil Berber, Gulsen Turkoglu. Specific and non-specific interaction effect on the solvatochromism of some symmetric (2-hydroxybenzilydeamino) phenoxy Schiff base derivatives. J Mol Liq 2016; 215:691–703

  51. Sidir I, Gulseven SY (2015) Estimation of ground and excited state dipole moments of oil red O by solvatochromic shift methods. Spectrochim Acta Part A Mol Biomol Spectrosc 135:560–567

    Article  CAS  Google Scholar 

  52. Takjoo R, Centore R (2013) Synthesis, X-ray structure, spectroscopic properties and DFT studies of some dithiocarbazate complexes of nickel (II). J Mol Struct 1031:180–185

    Article  CAS  Google Scholar 

  53. Nagarajan N, Velmurugan G, Prabhu G, Venuvanalingam P, Renganathan R (2014) A combined experimental and theoretical investigation of imidazole – carbazole fluorophores. J Lumin 147:111–120

    Article  CAS  Google Scholar 

  54. Pereira TM, Vitorio F, Amaral RC, Zanoni KPS, Iha NYM, Kummerle AE (2016) Microwave-assisted synthesis and photophysical studies of novel fluorescent N-acylhydrazone and semicarbazone-7-OH-coumarin dyes. New J Chem 40:8846–8854

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The author Y.F. Nadaf thankful to Mohamed Zikriya, Promod A. G and Anilkumar Research Scholars from Bangalore University, Bangalore for assisting the preparation of this manuscript.

Author information

Authors and Affiliations

  1. Department of Physics, Bangalore University, Jnanabharathi Campus, Bengaluru, 560056, India

    C. G. Renuka

  2. Department of Physics and Research Center, Maharani Science College for Women, Bengaluru, 560001, India

    Y. F. Nadaf & G. Sriprakash

  3. Department of Chemistry, University of Mysore, Mysuru, 570005, India

    S. Rajendra Prasad

Authors
  1. C. G. Renuka
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Y. F. Nadaf
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. G. Sriprakash
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. S. Rajendra Prasad
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Y. F. Nadaf.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Renuka, C.G., Nadaf, Y.F., Sriprakash, G. et al. Solvent Dependence on Structure and Electronic Properties of 7-(Diethylamino) - 2H -1- Benzopyran-2- one (C-466) Laser Dye. J Fluoresc 28, 839–854 (2018). https://doi.org/10.1007/s10895-018-2249-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10895-018-2249-9

Keywords

Search

Navigation