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Properties, aromaticity, and substituents effects in poly nitro- and amino-substituted benzenes

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Abstract

Geometrical parameters, aromaticity, and conformational flexibility of the set of polysubstituted benzenes with different number and position of nitro and amino groups were calculated at the MP2/cc-pvdz level of theory. The key factor for structural and energetic changes has been identified. This is related to the presence of nitro and amino groups in vicinal positions that forms strong intramolecular resonance-assisted hydrogen bonds with a binding energy of 7–14 kcal/mol. Increasing number of such bonds facilitates a cooperative effect, inducing notable changes in molecular geometry (particularly increasing bond alternation within H2N–C–C–NO2 fragment and planarization of amino group), drastic increasing of conformational flexibility and decreasing of aromaticity. In spite of well-known π-electron effects of nitro and amino substituents, influence of their push–pull interaction through aromatic moiety is negligible compared to the effect of the hydrogen bonding. That results in great difference of the ortho-isomers as compared to meta- and para-isomers.

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Acknowledgments

The use of trade, product, or firm names in this report is for descriptive purposes only and does not imply endorsement by the U.S. Government. Results in this study were funded and obtained from research conducted under the Environmental Quality Technology Program of the United States Army Corps of Engineers by the USAERDC. Permission was granted by the Chief of Engineers to publish this information. The findings of this report are not to be construed as an official Department of the Army position unless so designated by other authorized documents.

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Authors and Affiliations

  1. STC’Institute for Single Crystals, National Academy of Sciences of Ukraine, 60 Lenina Ave, Kharkiv, 61001, Ukraine

    Irina V. Omelchenko & Oleg V. Shishkin

  2. V.N. Karazin Kharkiv National University, 4 Svobody sq, Kharkiv, 61077, Ukraine

    Oleg V. Shishkin

  3. Badger Technical Services, LLC, Vicksburg, MS, USA

    Leonid Gorb

  4. US Army ERDC, 3532 Manor Dr, Vicksburg, MS, 39180, USA

    Frances C. Hill & Jerzy Leszczynski

  5. Interdisciplinary Center for Nanotoxicity, Department of Chemistry and Biochemistry, Jackson State University, P.O. Box 17910, 1325 Lynch Street, Jackson, MS, 39217, USA

    Jerzy Leszczynski

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  1. Irina V. Omelchenko
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  2. Oleg V. Shishkin
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  3. Leonid Gorb
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Correspondence to Irina V. Omelchenko.

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Omelchenko, I.V., Shishkin, O.V., Gorb, L. et al. Properties, aromaticity, and substituents effects in poly nitro- and amino-substituted benzenes. Struct Chem 23, 1585–1597 (2012). https://doi.org/10.1007/s11224-012-9971-8

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  • DOI: https://doi.org/10.1007/s11224-012-9971-8

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