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Synthesis, Spectroscopic and Computational Studies of Charge-Transfer Complexation Between 4-Aminoaniline and 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone

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Abstract

A charge-transfer (CT) complex that forms from the reaction of the donor 4-amino aniline (4AA) and the π-acceptor 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) have been studied and characterized experimentally and as well as theoretically at room temperature. The experimental work includes the application of UV–visible spectroscopy to identify the CT band of the CT-complex. The composition of the complex has been investigated using spectrophotometric titration and Job’s method of continuous variation and found to be 1:1. Furthermore, to calculate the formation constant and molar extinction coefficient, we have used the Benesi–Hildebrand equation. Infrared, 1H NMR, 13C NMR and mass spectral studies were used to characterize and confirm the formation of the CT-complex. The experimental studies were supported by quantum chemical simulations using density functional theory. The computational analysis of molecular geometry, Mulliken charges, and molecular electrostatic potential surfaces of reactants and complexes are helpful in assigning the CT route. The C=O bond length of DDQ increased upon complexation with 4AA. We have also observed that a substantial amount of charge has been transferred from 4AA to DDQ in the process of complexation. An excellent consistency has been achieved between experimental and theoretical results.

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Acknowledgements

One of authors AL is thankful to UGC, New Delhi for providing a fellowship, and to The Head, Department of Chemistry, Osmania University, for providing the facilities for the work. Funding was provided by University Grants Commission (Grant No. F.4-1/2006(BSR)11-38/2008(BSR)/2014-2015/02).

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  1. Department of Chemistry, Osmania University, Hyderabad, 500007, India

    Arunapriya Lakkadi, Naveen Baindla & Parthasarathy Tigulla

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  1. Arunapriya Lakkadi
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Correspondence to Parthasarathy Tigulla.

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Lakkadi, A., Baindla, N. & Tigulla, P. Synthesis, Spectroscopic and Computational Studies of Charge-Transfer Complexation Between 4-Aminoaniline and 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone. J Solution Chem 46, 2171–2190 (2017). https://doi.org/10.1007/s10953-017-0685-9

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