-Comparison of σ/ π-hole aerogen-bonding interactions based on C2H4···NgOX2 (Ng = Kr, Xe; X = F, Cl, Br) complexes

Yiqiang Deng; Zanzhang; Weiliang Cao; Yuan Liu; Baishu Zheng; Zhaoxu Wang

doi:10.1007/s00894-022-05290-w

^-Comparison of σ/ π-hole aerogen-bonding interactions based on C₂H₄···NgOX₂ (Ng = Kr, Xe; X = F, Cl, Br) complexes

J Mol Model. 2022 Oct 3;28(11):339. doi: 10.1007/s00894-022-05290-w.

Authors

Yiqiang Deng¹, Zanzhang², Weiliang Cao³, Yuan Liu⁴, Baishu Zheng², Zhaoxu Wang⁵

Affiliations

¹ College of Chemical Engineering, Key Laboratory of Inferior Crude Oil Upgrade Processing of Guangdong Provincial Higher Education Institutes, Guangdong, Guangdong University of Petrochemical Technology, Maoming, 525000, Guangdong, China.
² Key Laboratory of Theoretical Organic Chemistry and Function Molecule of Ministry of Education, Hunan Provincial Key Laboratory of Controllable Preparation and Functional Application of Fine Polymers, School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan, 411201, China.
³ Hainan Vocational University of Science and Technology, Hainan, 571126, China.
⁴ Key Laboratory of Theoretical Organic Chemistry and Function Molecule of Ministry of Education, Hunan Provincial Key Laboratory of Controllable Preparation and Functional Application of Fine Polymers, School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan, 411201, China. milehigh1860@hotmail.com.
⁵ Key Laboratory of Theoretical Organic Chemistry and Function Molecule of Ministry of Education, Hunan Provincial Key Laboratory of Controllable Preparation and Functional Application of Fine Polymers, School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan, 411201, China. hnust_chem@163.com.

PMID: 36190570
DOI: 10.1007/s00894-022-05290-w

Abstract

The geometric structure, energy properties, and electronic properties of the aerogen-bonding interaction formed by C₂H₄ and NgOX₂ (Ng = Kr, Xe; X = F, Cl, Br) have been studied at the B2PLYP-D3(BJ)/ aug-cc-pVTZ (PP) level. Two kinds of aerogen-bonding interactions were observed among the title systems: the σ-hole and the π-hole complexes. The σ-hole aerogen-bonding complex has a binding energy in the range of - 6.29 ~ - 8.17 kcal/mol, which is the most stable. The binding energies of C₂H₄···NgOX₂ increased as X = F < Cl < Br and Ng = KrOX₂ < XeOX₂ for the σ/π-hole aerogen-bonding complexes. The atoms in molecules (AIM), the non-covalent interaction (NCI) index, and the LMO-EDA energy decomposition analysis were adopted to study the nature of the σ/π-hole aerogen-bonding interaction. The results show that the electrostatic term contributes the most to the total interaction energy for the σ/π-hole aerogen-bonding complexes.

Keywords: AIM,; Aerogen-bonding interaction,; LMO-EDA energy decomposition; Non-covalent interaction (NCI) index,.

Abstract

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