Charge-Shift Bonding Propensity in Halogen-Bonded BXY (B Is a Small Lewis Base H<sub>2</sub>O or NH<sub>3</sub>; X and Y Are Halogen Atoms) Complexes: An NBO/NRT/AIM Investigation
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 i...
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MDPI AG
2023-08-01
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| Series: | Molecules |
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| author | Junjie Song Mengyang Wang Xiaocheng Xu Qinghao Shao Ying Zhao Guiqiu Zhang Nan Sun |
| author_facet | Junjie Song Mengyang Wang Xiaocheng Xu Qinghao Shao Ying Zhao Guiqiu Zhang Nan Sun |
| author_sort | Junjie Song |
| collection | DOAJ |
| description | 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 H<sub>2</sub>O or NH<sub>3</sub>; 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 NH<sub>3</sub>ClF, NH<sub>3</sub>BrF, and NH<sub>3</sub>IF). 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. |
| first_indexed | 2024-03-10T23:18:00Z |
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| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T23:18:00Z |
| publishDate | 2023-08-01 |
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| spelling | doaj.art-f5635de06c8b48dcabd443dd0287b2252023-11-19T08:32:51ZengMDPI AGMolecules1420-30492023-08-012817621210.3390/molecules28176212Charge-Shift Bonding Propensity in Halogen-Bonded BXY (B Is a Small Lewis Base H<sub>2</sub>O or NH<sub>3</sub>; X and Y Are Halogen Atoms) Complexes: An NBO/NRT/AIM InvestigationJunjie Song0Mengyang Wang1Xiaocheng Xu2Qinghao Shao3Ying Zhao4Guiqiu Zhang5Nan Sun6Key Laboratory of Molecular and Nano Probes, Ministry of Education, College of Chemistry, Chemical Engineering and Materials Science, Shandong Normal University, Jinan 250014, ChinaKey Laboratory of Molecular and Nano Probes, Ministry of Education, College of Chemistry, Chemical Engineering and Materials Science, Shandong Normal University, Jinan 250014, ChinaKey Laboratory of Organic Optoelectronics and Molecular Engineering of the Ministry of Education, Department of Chemistry, Tsinghua University, Beijing 100084, ChinaKey Laboratory of Molecular and Nano Probes, Ministry of Education, College of Chemistry, Chemical Engineering and Materials Science, Shandong Normal University, Jinan 250014, ChinaKey Laboratory of Molecular and Nano Probes, Ministry of Education, College of Chemistry, Chemical Engineering and Materials Science, Shandong Normal University, Jinan 250014, ChinaKey Laboratory of Molecular and Nano Probes, Ministry of Education, College of Chemistry, Chemical Engineering and Materials Science, Shandong Normal University, Jinan 250014, ChinaKey Laboratory of Molecular and Nano Probes, Ministry of Education, College of Chemistry, Chemical Engineering and Materials Science, Shandong Normal University, Jinan 250014, ChinaCharge-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 H<sub>2</sub>O or NH<sub>3</sub>; 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 NH<sub>3</sub>ClF, NH<sub>3</sub>BrF, and NH<sub>3</sub>IF). 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.https://www.mdpi.com/1420-3049/28/17/6212CS bonding propensityω-bondinghalogen bondingNBO/NRTAIM |
| spellingShingle | Junjie Song Mengyang Wang Xiaocheng Xu Qinghao Shao Ying Zhao Guiqiu Zhang Nan Sun Charge-Shift Bonding Propensity in Halogen-Bonded BXY (B Is a Small Lewis Base H<sub>2</sub>O or NH<sub>3</sub>; X and Y Are Halogen Atoms) Complexes: An NBO/NRT/AIM Investigation Molecules CS bonding propensity ω-bonding halogen bonding NBO/NRT AIM |
| title | Charge-Shift Bonding Propensity in Halogen-Bonded BXY (B Is a Small Lewis Base H<sub>2</sub>O or NH<sub>3</sub>; X and Y Are Halogen Atoms) Complexes: An NBO/NRT/AIM Investigation |
| title_full | Charge-Shift Bonding Propensity in Halogen-Bonded BXY (B Is a Small Lewis Base H<sub>2</sub>O or NH<sub>3</sub>; X and Y Are Halogen Atoms) Complexes: An NBO/NRT/AIM Investigation |
| title_fullStr | Charge-Shift Bonding Propensity in Halogen-Bonded BXY (B Is a Small Lewis Base H<sub>2</sub>O or NH<sub>3</sub>; X and Y Are Halogen Atoms) Complexes: An NBO/NRT/AIM Investigation |
| title_full_unstemmed | Charge-Shift Bonding Propensity in Halogen-Bonded BXY (B Is a Small Lewis Base H<sub>2</sub>O or NH<sub>3</sub>; X and Y Are Halogen Atoms) Complexes: An NBO/NRT/AIM Investigation |
| title_short | Charge-Shift Bonding Propensity in Halogen-Bonded BXY (B Is a Small Lewis Base H<sub>2</sub>O or NH<sub>3</sub>; X and Y Are Halogen Atoms) Complexes: An NBO/NRT/AIM Investigation |
| title_sort | charge shift bonding propensity in halogen bonded bxy b is a small lewis base h sub 2 sub o or nh sub 3 sub x and y are halogen atoms complexes an nbo nrt aim investigation |
| topic | CS bonding propensity ω-bonding halogen bonding NBO/NRT AIM |
| url | https://www.mdpi.com/1420-3049/28/17/6212 |
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