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Physical Sciences Reviews

Ed. by Giamberini, Marta / Jastrzab, Renata / Liou, Juin J. / Luque, Rafael / Nawab, Yasir / Saha, Basudeb / Tylkowski, Bartosz / Xu, Chun-Ping / Cerruti, Pierfrancesco / Ambrogi, Veronica / Marturano, Valentina / Gulaczyk, Iwona

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Substituent effects on linear and nonlinear optical properties of fluorescent (E)-2-(4-halophenyl)-7-arlstyrylimidazo[1,2-A]
pyridine: spectroscopic and computational methods

Siddheshwar D. Jadhav
  • Department of Dyestuff Technology, Institute of Chemical Technology, N. P. Marg, Matunga, Mumbai (MH) 40001, India
  • Other articles by this author:
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/ Ponnadurai Ramasami
  • Computational Chemistry Group, Department of Chemistry, Faculty of Science, University of Mauritius, Réduit 80837, USA
  • Department of Applied Chemistry, University of Johannesburg, Doornfontein, Johannesburg 2028, South Africa
  • Other articles by this author:
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/ Nagaiyan Sekar
  • Corresponding author
  • Department of Dyestuff Technology, Institute of Chemical Technology, N. P. Marg, Matunga, Mumbai (MH) 40001, India
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Published Online: 2018-10-10 | DOI: https://doi.org/10.1515/psr-2018-0032

Abstract

Effects of alkylamino and bromo substituents on imidazo[1,2-a]pyridines containing donor-π-acceptor type groups were comprehensively investigated for their linear and nonlinear optical properties by solvatochromic and DFT (CAM-B3LYP and BHandHLYP) methods. The difference between the ground and excited dipole moments as well as their ratios obtained by solvatochromic analysis indicate that the excited state is more polar than the ground state for both the bromo and diethyl amino derivative. More than twofold enhancement in the excited state dipole moments was observed as revealed by the difference and ratio of dipole moment upon the introduction of alkylamino donor group and these suggest large intramolecular charge transfer in the dyes. Stabilization energy above 20kJ/mol was observed for large number of electron donor–acceptor interactions in Natural Bonding Orbital (NBO) analysis. Bond length alternation (BLA) and Bond order alternation (BOA) values tend to zero suggesting a high degree of polarization in the dyes. Enhancement in mean polarizability (α0), first hyperpolarizability (β0) and second static hyperpolarizabilities (γˉ) were observed by the introduction of alkylamino and bromo group in place of chloro in spite of the fact that Hammett constant of chloro and bromo are the same. The dyes have fundamental and intrinsic properties within the Hamiltonian limits. The two-photon absorption cross section value (≈100GM) is comparable with LDS-698, a commercial TPA dye. This investigation is important for understanding the electronic structure of imidazo[1,2-a]pyridine with active functional groups and extending the potential for optical applications.

This article offers supplementary material which is provided at the end of the article.

Keywords: Imidazo[1,2-a]pyridine; DFT; TDDFT; fundamental limits; two photon absorption; NLO properties

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Published Online: 2018-10-10


Citation Information: Physical Sciences Reviews, Volume 4, Issue 4, 20180032, ISSN (Online) 2365-659X, DOI: https://doi.org/10.1515/psr-2018-0032.

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