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Red Emitting Coumarins: Insights of Photophysical Properties with DFT Methods

Journal of Fluorescence volume 25, pages 1117–1126 (2015)Cite this article

Abstract

Red emitting dyes are of interest in various technological applications. Coumarins, though being an important class of fluorescent molecules, those with red emission, have been rarely studied theoretically. The structural and electronic aspects of three novel red emitting coumarins were studied using DFT and TD-DFT methods. The functionals employed were the hybrid functionals B3LYP, CAM-B3LYP, PBE0 and the highly parameterized empirical functional M06. The geometry at ground state reveals the electron donor N,N-diethylamino group is coplanar with the chromophoric system and the nitrile group induces a red shift to the absorption and emission. The electronic energies and dipole moments were solvent dependent. The basis sets and functionals were benchmarked for their performance with these molecules. B3LYP has been proved to be more efficient in computations whereas the basis sets do not have noticeable effect on the electronic properties. However, adding a polarization function to the basis set has improved the calculation of vertical excitation. The B3LYP functional gives maximum absolute deviation of 0.20 eV in calculating the vertical excitations and 0.18 eV for emission.

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Acknowledgments

Abhinav Tathe is thankful to University Grants Comission, New Delhi (India) for fellowship. LR and PR would like to acknowledge the facilities from the University of Mauritius

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Affiliations

  1. Tinctorial Chemistry Group, Department of Dyestuff Technology, Institute of Chemical Technology, N. P. Marg, Matunga, Mumbai, MH, 400019, India

    Abhinav B. Tathe & Nagaiyan Sekar

  2. Computational Chemistry Group, Department of Chemistry, Faculty of Science, University of Mauritius, Réduit, 80837, Mauritius

    Lydia Rhyman & Ponnadurai Ramasami

  3. Department of Pharmaceutical Chemistry, Faculty of Pharmacy, King Saud University, P.O. Box 2457, Riyadh, 11451, Saudi Arabia

    Ponnadurai Ramasami

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  1. Abhinav B. Tathe
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  2. Lydia Rhyman
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  4. Nagaiyan Sekar
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Correspondence to Nagaiyan Sekar.

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Tathe, A.B., Rhyman, L., Ramasami, P. et al. Red Emitting Coumarins: Insights of Photophysical Properties with DFT Methods. J Fluoresc 25, 1117–1126 (2015). https://doi.org/10.1007/s10895-015-1602-5

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  • DOI: https://doi.org/10.1007/s10895-015-1602-5

Keywords

  • Coumarins
  • DFT
  • TD-DFT
  • Vertical excitation