A theoretical study of the global and local electrophilicity, nucleophilicity, polarizability and QTAIM theory for calix[4]arene-gas interaction

B Gassoumi; H Ghalla; R Ben Chaabane

doi:10.1016/j.heliyon.2020.e04554

A theoretical study of the global and local electrophilicity, nucleophilicity, polarizability and QTAIM theory for calix[4]arene-gas interaction

Heliyon. 2020 Jul 31;6(7):e04554. doi: 10.1016/j.heliyon.2020.e04554. eCollection 2020 Jul.

Authors

B Gassoumi^{1

2}, H Ghalla³, R Ben Chaabane¹

Affiliations

¹ Laboratory of Advanced Materials and Interfaces (LIMA), University of Monastir, Faculty of Science of Monastir, Avenue of Environnment, 5000, Monastir, Tunisia.
² Institute of Light and Matter, UMR5306 University of Lyon 1-CNRS, University of Lyon, 69622, Villeurbanne Cedex, France.
³ University of Monastir, Quantum and Statistical Physics Laboratory, Faculty of Science, Monastir, 5079, Tunisia.

Abstract

The calix[4]arene molecule, abbreviated as CX[4], is known by the four phenolic groups and a hydrophobic cavity able to enclose small molecules. The interactions between CX[4] and NO_3, NO₂, CO₂, and N₂ gas molecules have been studied. These guest species are placed inside and outside the cavity of the host molecule CX[4]. The formation of H-bonding has been deeply discussed based on the infrared spectrum and the polarizability analysis. Global and local indices have been calculated for a series of gas (NO_3, NO₂, CO₂ and N₂) in interaction with the CX[4] molecule to explain the electrophilic or nucleophilic activations in endo-vs. exo-cavity interaction zone. As expected, there is a correlation between the proposed global electrophilicity and global nucleophilicity together for an explanation of the chemo-selectivity region. Finally, the topological parameter analyses of the host-guests interactions have been estimated by using DFT calculations.

Keywords: Calix[4]arene; Electro-philic and nucleophilic sites; Hydrogen bond; Interaction energies; Physical chemistry; Polarizability; Theoretical chemistry.