ISOMERIC PERFLUOROCORROLES AS PEERSPECTIVE MACROCYCLIC LIGANDS: GEOMETRIC, ELECTRONIC AND THERMODYNAMICAL CHARACTERISTICS OF MOLECULAR STRUCTURES IN THE FRAMEWORK OF DENSITY FUNCTIONAL THEORY
Rubrics: 1. CHEMISTRY
Authors:
1.
KNITU
2.
Nacional'nyy Issledovatel'skiy Centr “Kurchatovskiy Institut”
Type:
Article
Pages:
from 12
to 21
Status:
Published
Received:
10.03.2026
Accepted:
15.04.2026
Published:
05.05.2026
Language:
Russian
Keywords:
CORROLE, MOLECULAR STRUCTURE, THERMODYNAMICAL PARAMETER, DFT
Abstract:
Using the density functional theory (DFT) with the M06 functional and the def2TZVP basis set, in combination with the inclusion of dispersion interactions via the D3 version of the Grimme dispersion, the molecular structures of perfluorocorrole(1.1.1.0) and nine of its structural isomers, namely perfluorocorrole(1.1.1.0) (A), perfluorocorrole(1.1.1.0) (B), perfluorocorrole(1.0.0.2) (A), perfluorocorrole(1.0.0.2) (B), perfluorocorrole(1.0.0.2) (C), perfluorocorrole(1.0.0.2) (D), perfluorocorrole(2.0.1.0) (A), perfluorocorrole(2.0.1.0) (B), perfluorocorrole(3.0.0.0) and perfluorocorrole (3.0.0.0) (B) were calculated. It was found that perfluorocorrole (1.1.1.0) (A) is the most energetically favorable among them, although the difference between it and the closest structural compound perfluorocorrole (1.1.1.0) (B) according to this parameter is less than 2 kJ/mol. The least favorable is perfluorocorrole (3.0.0.0) (A), the total energy of which is almost 200 kJ/mol higher. The standard enthalpies fH 0 , standard entropies S 0f and standard Gibbs energies fG 0 of formation of these compounds were calculated, the values of the most important bond lengths, valence and non-valence angles in them are presented. It was noted that in almost all of these isomers, both the groups of four nitrogen atoms and the 15-membered macrocycles containing these atoms are non-coplanar, with some cases deviating significantly from coplanarity. Furthermore, all four interatomic distances between adjacent nitrogen atoms in any of these compounds are different, as are the non-bonded angles between these atoms. NBO analysis of all of the above-mentioned isomers was also performed, revealing a high degree of delocalization of electron density in these compounds.
Using the density functional theory (DFT) with the M06 functional and the def2TZVP basis set, in combination with the inclusion of dispersion interactions via the D3 version of the Grimme dispersion, the molecular structures of perfluorocorrole(1.1.1.0) and nine of its structural isomers, namely perfluorocorrole(1.1.1.0) (A), perfluorocorrole(1.1.1.0) (B), perfluorocorrole(1.0.0.2) (A), perfluorocorrole(1.0.0.2) (B), perfluorocorrole(1.0.0.2) (C), perfluorocorrole(1.0.0.2) (D), perfluorocorrole(2.0.1.0) (A), perfluorocorrole(2.0.1.0) (B), perfluorocorrole(3.0.0.0) and perfluorocorrole (3.0.0.0) (B) were calculated. It was found that perfluorocorrole (1.1.1.0) (A) is the most energetically favorable among them, although the difference between it and the closest structural compound perfluorocorrole (1.1.1.0) (B) according to this parameter is less than 2 kJ/mol. The least favorable is perfluorocorrole (3.0.0.0) (A), the total energy of which is almost 200 kJ/mol higher. The standard enthalpies fH 0 , standard entropies S 0f and standard Gibbs energies fG 0 of formation of these compounds were calculated, the values of the most important bond lengths, valence and non-valence angles in them are presented. It was noted that in almost all of these isomers, both the groups of four nitrogen atoms and the 15-membered macrocycles containing these atoms are non-coplanar, with some cases deviating significantly from coplanarity. Furthermore, all four interatomic distances between adjacent nitrogen atoms in any of these compounds are different, as are the non-bonded angles between these atoms. NBO analysis of all of the above-mentioned isomers was also performed, revealing a high degree of delocalization of electron density in these compounds.
Keywords:
CORROLE, MOLECULAR STRUCTURE, THERMODYNAMICAL PARAMETER, DFT
CORROLE, MOLECULAR STRUCTURE, THERMODYNAMICAL PARAMETER, DFT
