Computational Insight into the Nature and Strength of the π-Hole Type Chalcogen∙∙∙Chalcogen Interactions in the XO2∙∙∙CH3YCH3 Complexes (X = S, Se, Te; Y = O, S, Se, Te)
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Published:2023-11-10
Issue:22
Volume:24
Page:16193
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ISSN:1422-0067
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Container-title:International Journal of Molecular Sciences
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language:en
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Short-container-title:IJMS
Author:
Lei Fengying1,
Liu Qingyu1,
Zhong Yeshuang1,
Cui Xinai1,
Yu Jie1,
Hu Zuquan1ORCID,
Feng Gang2ORCID,
Zeng Zhu1ORCID,
Lu Tao1
Affiliation:
1. School of Basic Medical Sciences/School of Biology and Engineering, Guizhou Medical University, Guiyang 550025, China
2. School of Chemistry and Chemical Engineering, Chongqing University, Daxuecheng South Rd. 55, Chongqing 401331, China
Abstract
In recent years, the non-covalent interactions between chalcogen centers have aroused substantial research interest because of their potential applications in organocatalysis, materials science, drug design, biological systems, crystal engineering, and molecular recognition. However, studies on π-hole-type chalcogen∙∙∙chalcogen interactions are scarcely reported in the literature. Herein, the π-hole-type intermolecular chalcogen∙∙∙chalcogen interactions in the model complexes formed between XO2 (X = S, Se, Te) and CH3YCH3 (Y = O, S, Se, Te) were systematically studied by using quantum chemical computations. The model complexes are stabilized via one primary X∙∙∙Y chalcogen bond (ChB) and the secondary C−H∙∙∙O hydrogen bonds. The binding energies of the studied complexes are in the range of −21.6~−60.4 kJ/mol. The X∙∙∙Y distances are significantly smaller than the sum of the van der Waals radii of the corresponding two atoms. The X∙∙∙Y ChBs in all the studied complexes except for the SO2∙∙∙CH3OCH3 complex are strong in strength and display a partial covalent character revealed by conducting the quantum theory of atoms in molecules (QTAIM), a non-covalent interaction plot (NCIplot), and natural bond orbital (NBO) analyses. The symmetry-adapted perturbation theory (SAPT) analysis discloses that the X∙∙∙Y ChBs are primarily dominated by the electrostatic component.
Funder
National Natural Science Foundation of China
Natural Science Foundation of Guizhou Province
Youth Science and Technology Talents Growth Project of Guizhou Ordinary Colleges and Universities
Science and Technology Fund Project of Guizhou Provincial Health Commission
High-Level Talent Initiation Project of Guizhou Medical University
Subject
Inorganic Chemistry,Organic Chemistry,Physical and Theoretical Chemistry,Computer Science Applications,Spectroscopy,Molecular Biology,General Medicine,Catalysis