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DFT Calculations of Some Important Radicals Used in the Nitroxide-Mediated Polymerization and Their HOMO‒LUMO, Natural Bond Orbital, and Molecular Electrostatic Potential Comparative Analysis

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Abstract

Nitroxide radicals are important organic compounds, the stability of which is governed by a degree of delocalization of an unpaired electron and steric hindrances in their molecules. The most stable radicals can be identified by theoretical methods. The B3PW91/6-31G + (d, p) density functional theory calculation for the 2,2,5,5-tetramethylpyrrolidine-N-oxyl nitroxide, (2,2,6,6-tetramethylpiperidin-1-yl)oxyl, (2,2,8,8-tetramethyl-4-oxoazocan-1-yl)oxidanyl, 1,1,3,3-tetramethylisoindolin-N-oxyl nitroxide, 2,2,10,10-tetraethyl-isoindolin-N-oxyl, di-tert-buthyl nitroxide, 2,2,5,5-tetramethyl-4-phenyl-3-azahexane-N-oxyl, and N-(2-methylpropyl)-N-(1-diethyl-phosphono-2,2-dimethylpropyl)-N-oxyl nitroxide radicals has been made. The FTIR and UV–Vis vibrational frequencies have been calculated by the same method. It is shown that the shortest N‒O bond length (1.2684 Å) is observed in the 1,1,3,3-tetramethylisoindolin-N-oxyl nitroxide radical. It has been found that the most stable of the investigated radicals is 2,2,10,10-tetraethyl-isoindolin-N-oxyl, which is indicated by the low EHOMO‒LUMO value for this substance. For all the examined nitroxides, the electron density, electrostatic potential surfaces, and natural bond orbital data have been obtained. The natural bond orbital analysis has confirmed the electron density delocalization within the nitroxide radicals.

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ACKNOWLEDGMENTS

The authors would like to thank the Bingöl University for providing the server and the Bitlis Eren University for providing the Gaussian software.

Funding

This study was carried out in part within the plan no. 0287-2021-0017 for the Institute of Chemistry and Chemical Technology, Siberian Branch of the Russian Academy of Sciences.

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Authors and Affiliations

  1. University of Bingöl, Vocational School of Food, Agriculture and Livestock, 12000, Bingöl, Turkey

    Feride Akman

  2. Institute of Chemistry and Chemical Technology, Krasnoyarsk Science Center, Siberian Branch, Russian Academy of Sciences, 660036, Krasnoyarsk, Russia

    Aleksandr S. Kazachenko

  3. Siberian Federal University, 660041, Krasnoyarsk, Russia

    Aleksandr S. Kazachenko

  4. Laboratory of Quantum and Statistical Physics (LR18ES18), Faculty of Sciences, University of Monastir, Monastir, Tunisia

    Noureddine Issaoui

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  1. Feride Akman
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Feride Akman, Kazachenko, A.S. & Issaoui, N. DFT Calculations of Some Important Radicals Used in the Nitroxide-Mediated Polymerization and Their HOMO‒LUMO, Natural Bond Orbital, and Molecular Electrostatic Potential Comparative Analysis. Polym. Sci. Ser. B 64, 765–777 (2022). https://doi.org/10.1134/S156009042270035X

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