INTERRELATION BETWEEN THE PERIPHERAL SUBSTITUTION ARCHITECTURE OF THE FREE BASE CORROLES AND MACROCYCLE AROMATICITY

UDC 535.37+541.65+543.4

  • Klenitsky Dmitry Vikentievich − PhD (Physics and Mathematics), Associate Professor, Assistant Professor, the Department of Physics. Belarusian State Technological University (13a, Sverdlova str., 220006, Minsk, Republic of Belarus). E-mail: klen@belstu.by

  • Gladkov Lev L’vovich − DSc (Physics and Mathematics), Associate Professor, Professor, the Department of Higher Math. Belarusian State Academy of Communications (8/2, F. Skorina str., 220114, Minsk, Republic of Belarus). E-mail: llglad@tut.by

  • Vershilovskaya Irina Vatslavovna − PhD (Biology), Senior Lecturer, the Department of Physics. Belarusian State Technological University (13a, Sverdlova str., 220006, Minsk, Republic of Belarus). E-mail: vi_va@tut.by

  • Maes Wouter − PhD (Chemistry), Professor. Hasselt University (B-3590, Diepenbeek, Belgium). E-mail: wouter.maes@uhasselt.be

  • Kruk Mikalai Mikalaevich − DSc (Physics and Mathematics), Associate Professor, Head of the Department of Physics. Belarusian State Technological University (13a, Sverdlova str., 220006, Minsk, Republic of Belarus). E-mail: m.kruk@belstu.by

DOI: https://doi.org/10.52065/2520-6141-2022-260-2-43-48

Key words: corrole, NH-tautomers, aromaticity, peripheral substitution.

For citation: Klenitsky D. V., Gladkov L. L., Vershilovskaya I. V., Maes W. Kruk M. M. Interrelation Relation between the peripheral substitution architecture of the free base corroles and macrocycle aromaticity. Proceedings of BSTU, issue 3, Physics and Mathematics. Informatics, 2022, no. 2 (260), pp. 43–48 (In Russian). DOI: https://doi.org/10.52065/2520-6141-2022-260-2-43-48.

Abstract

Using the harmonic oscillator model for aromaticity (HOMA), the aromaticity indices IHOMA for the macrocycle of two NH-tautomers of free base corroles with different peripheral substitution architectures were calculated. The molecular conformation of the long-wavelength T1 and short-wavelength T2 NH tautomers of the studied compounds was calculated by the density functional method. It was shown that the shape of the dominating 18-membered contour of the π-conjugation of the T2 tautomer is the same for all the studied corrole derivatives, while the shape of the dominating conjugation contour of the T1 tautomer differs depending on the architecture of the peripheral substitution. It has been established that the value of the aromaticity index IHOMA depends on the nature of the electronic communication between the macrocycle and peripheral substituents. The attachment of electron-donating substituents to the Cb-positions of the macrocycle leads to a decrease in the aromaticity of each of the two NH-tautomers. The value of the aromaticity index IHOMA decreases in proportion to the sum of the Hammett resonance constants σR of the peripheral substituents. It is proposed that this dependence can be used as a basis for controlling the aromaticity of the free base corroles macrocycle.

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05.05.2022