Charge-Shift Bonding Propensity in Halogen-Bonded BXY (B Is a Small Lewis Base H2O or NH3; X and Y Are Halogen Atoms) Complexes: An NBO/NRT/AIM Investigation

Junjie Song; Mengyang Wang; Xiaocheng Xu; Qinghao Shao; Ying Zhao; Guiqiu Zhang; Nan Sun

doi:10.3390/molecules28176212

Molecules (Aug 2023)

Charge-Shift Bonding Propensity in Halogen-Bonded BXY (B Is a Small Lewis Base H2O or NH3; X and Y Are Halogen Atoms) Complexes: An NBO/NRT/AIM Investigation

Junjie Song,
Mengyang Wang,
Xiaocheng Xu,
Qinghao Shao,
Ying Zhao,
Guiqiu Zhang,
Nan Sun

Affiliations

Junjie Song: Key Laboratory of Molecular and Nano Probes, Ministry of Education, College of Chemistry, Chemical Engineering and Materials Science, Shandong Normal University, Jinan 250014, China
Mengyang Wang: Key Laboratory of Molecular and Nano Probes, Ministry of Education, College of Chemistry, Chemical Engineering and Materials Science, Shandong Normal University, Jinan 250014, China
Xiaocheng Xu: Key Laboratory of Organic Optoelectronics and Molecular Engineering of the Ministry of Education, Department of Chemistry, Tsinghua University, Beijing 100084, China
Qinghao Shao: Key Laboratory of Molecular and Nano Probes, Ministry of Education, College of Chemistry, Chemical Engineering and Materials Science, Shandong Normal University, Jinan 250014, China
Ying Zhao: Key Laboratory of Molecular and Nano Probes, Ministry of Education, College of Chemistry, Chemical Engineering and Materials Science, Shandong Normal University, Jinan 250014, China
Guiqiu Zhang: Key Laboratory of Molecular and Nano Probes, Ministry of Education, College of Chemistry, Chemical Engineering and Materials Science, Shandong Normal University, Jinan 250014, China
Nan Sun: Key Laboratory of Molecular and Nano Probes, Ministry of Education, College of Chemistry, Chemical Engineering and Materials Science, Shandong Normal University, Jinan 250014, China

DOI: https://doi.org/10.3390/molecules28176212
Journal volume & issue: Vol. 28, no. 17
p. 6212

Abstract

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Charge-shift (CS) bonding is a new bonding paradigm in the field of chemical bonds. Our recent study has revealed that certain Cu/Ag/Au-bonds display both CS bonding and ω-bonding characters. In this investigation, we extend our study to halogen bonding. Our focus is on scrutinizing the CS bonding in halogen-bonded BXY (B is a small Lewis base H2O or NH3; X and Y are halogen atoms) complexes by using natural bond orbital (NBO) analysis, natural resonance theory (NRT), and atoms in molecules (AIM) methods. The primary objective is to establish a connection between halogen bonding (B–X) in BXY and CS bonding in free XY (di-halogens). The calculations indicate that the studied BXY can be classified into two types. One type with a weak halogen bond shows closed-shell interaction. The other type with a stronger B–X interaction exhibits both CS bonding and ω-bonding characters (as seen in NH3ClF, NH3BrF, and NH3IF). Another interesting finding is a novel propensity that the CS bonding in free XY tends to carry over the halogen bonding in BXY, and the same propensity is found in Cu/Ag/Au ω-bonded species. The present study may offer an approach to probe CS bonding in many more 3c/4e ω-bonded molecules.

Published in Molecules

ISSN: 1420-3049 (Online)
Publisher: MDPI AG
Country of publisher: Switzerland
LCC subjects: Science: Chemistry: Organic chemistry
Website: http://www.mdpi.com/journal/molecules

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