Physicochemical properties of the three-cavity form of calix[n = 4, 6, 8]aren molecules: DFT investigation
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The shape, size and diameter of the cavities are one of the main factors which control the interactions of the calix[n]arene molecules with cation, anion or neutral guests in sensor applications. In this work, vibrational spectroscopy analysis, molecular electrostatic potential (MEP) surface, atom in molecules (AIM) and thermochemical properties were used to check the reorganizations of hydrogen bonds in such cavity shape for the improvement of physical proprieties of CX[n] molecules. We have demonstrated that the hydrogen bonds O···H and the angles O–H···O of CX[n = 4, 6, 8] play the role of the moderator or modifier of the cavity. MEP topography reveals that the cavity form of CX is less hydrophilic as compared to those of CX cavity. The QTAIM theory showed that CX and CX has a more symmetric and well-organized cavity than CX. It was also shown that the hydrogen bond enhanced the topographic parameters in CX[n] at the lower edge levels.
KeywordsCalix[n]arene Hydrogen bonding Cooperativity Molecular electrostatic potential Intermolecular interactions
The authors acknowledge financial support from the Tunisian’s Ministry of high education and scientific research. In this work, we were granted access to the HPC resources of the FLMSN, ‘Fédération Lyonnaise de Modélisation et Sciences Numériques’, partner of EQUIPEX EQUIP@MESO and to the ‘Centre de calcul CC-IN2P3’ at Villeurbanne, France.
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