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Estimation of Ground-State and Singlet Excited-State Dipole Moments of Substituted Schiff Bases Containing Oxazolidin-2-one Moiety through Solvatochromic Methods

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Abstract

Absorption and fluorescence studies on novel Schiff bases (E)-4-(4-(4-nitro benzylideneamino)benzyl)oxazolidin-2-one (NBOA) and (E)-4-(4-(4-chlorobenzylidene amino)benzyl)oxazolidin-2-one (CBOA) were recorded in a series of twelve solvents upon increasing polarity at room temperature. Large Stokes shift indicates bathochromic fluorescence band for both the molecules. The photoluminescence properties of Schiff bases containing electron withdrawing and donating substituents were analyzed. Intramolecular charge transfer behavior can be studied based on the influence of different substituents in Schiff bases. Changes in position and intensity of absorption and fluorescence spectra are responsible for the stabilization of singlet excited-states of Schiff base molecules with different substituents, in polar solvents. This is attributed to the Intramolecular charge transfer (ICT) mechanism. In case of electron donating (−Cl) substituent, ICT contributes largely to positive solvatochromism when compared to electron withdrawing (−NO2) substituent. Ground-state and singlet excited-state dipole moments of NBOA and CBOA were calculated experimentally using solvent polarity function approaches given by Lippert–Mataga, Bakhshiev, Kawskii-Chamma-Viallet and Reichardt. Due to considerable π- electron density redistribution, singlet excited-state dipole moment was found to be greater than ground-state dipole moment. Ground-state dipole moment value which was determined by quantum chemical method was used to estimate excited-state dipole moment using solvatochromic correlations. Kamlet-Abboud-Taft and Catalan multiple linear regression approaches were used to study non-specific solute-solvent interaction and hydrogen bonding interactions in detail. Optimized geometry and HOMO-LUMO energies of NBOA and CBOA have been determined by DFT and TD-DFT/PCM (B3LYP/6-311G (d, p)). Mulliken charges and molecular electrostatic potential have also been evaluated from DFT calculations.

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Acknowledgments

We wish to thank Sravan Kumar Perumalla, Department of IPC, IISc, Bengaluru, for providing the facility for Gaussian based computational studies. We thank NMR Centre, IISc, Bengaluru, India, Anthem Biosciences, Bengaluru, India and STIC, Cochin University of Science & Technology Cochin for the spectral analysis.

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  1. Department of Chemistry, Christ University, Bengaluru, 560 029, India

    Rekha Kumari, Anitha Varghese & Louis George

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  1. Rekha Kumari
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Correspondence to Anitha Varghese.

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Kumari, R., Varghese, A. & George, L. 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 (2017). https://doi.org/10.1007/s10895-016-1942-9

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