Insight from DFT Calculation on the Increasing Effect of the Cation-π Interaction on the Intramolecular Hydrogen Bond in Methyl Salicylate Complex with the Presence of Different Solvents

doi:10.1007/s40242-025-4229-3

摘要/Abstract

摘要： A comprehensive investigation is conducted in the present study to analyze the non-covalent interactions displayed by the methyl salicylate complex when exposed to various solvents. The density functional theory (DFT) method is utilized to explore the impact of cation-π interaction on the strength and characteristics of the intramolecular hydrogen bond (IMHB). The findings display an augmentation in the strength of cation-π interaction within the gas phase compared to the solution. The analyses of atoms in molecules (AIM) and the natural bond orbital (NBO) are employed to provide further information on the nature of the studied interactions. According to the findings, the HB present in the considered complex falls into the medium HBs category. In addition, our investigation indicates that the cation-π interaction reinforces the IMHB in diverse solvents, but the reverse is true for the gas phase. Finally, an evaluation of the electronic properties, stability, and reactivity of the complex is performed by investigating frontier molecular orbitals, such as energy gap, chemical hardness, and electronic chemical potential. The results of this study that are ubiquitous in biological systems may be useful for the design and synthesis of a variety of supramolecular complexes with the desired properties.

关键词: Methyl salicylate, Cation-π, Intramolecular hydrogen bond, Atom in molecule (AIM), Natural bond orbital (NBO)

Abstract: A comprehensive investigation is conducted in the present study to analyze the non-covalent interactions displayed by the methyl salicylate complex when exposed to various solvents. The density functional theory (DFT) method is utilized to explore the impact of cation-π interaction on the strength and characteristics of the intramolecular hydrogen bond (IMHB). The findings display an augmentation in the strength of cation-π interaction within the gas phase compared to the solution. The analyses of atoms in molecules (AIM) and the natural bond orbital (NBO) are employed to provide further information on the nature of the studied interactions. According to the findings, the HB present in the considered complex falls into the medium HBs category. In addition, our investigation indicates that the cation-π interaction reinforces the IMHB in diverse solvents, but the reverse is true for the gas phase. Finally, an evaluation of the electronic properties, stability, and reactivity of the complex is performed by investigating frontier molecular orbitals, such as energy gap, chemical hardness, and electronic chemical potential. The results of this study that are ubiquitous in biological systems may be useful for the design and synthesis of a variety of supramolecular complexes with the desired properties.

Key words: Methyl salicylate, Cation-π, Intramolecular hydrogen bond, Atom in molecule (AIM), Natural bond orbital (NBO)

Fahimeh ALIREZAPOUR, Kourosh BAMDAD, Yaghoob BABAMIR, Azadeh KHANMOHAMMADI. Insight from DFT Calculation on the Increasing Effect of the Cation-π Interaction on the Intramolecular Hydrogen Bond in Methyl Salicylate Complex with the Presence of Different Solvents[J]. 高等学校化学研究, 2025, 41(3): 545-556.

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