Details
| Originalsprache | Englisch |
|---|---|
| Seiten (von - bis) | 5150-5155 |
| Seitenumfang | 6 |
| Fachzeitschrift | Journal of Physical Chemistry Letters |
| Jahrgang | 12 |
| Frühes Online-Datum | 25 Mai 2021 |
| Publikationsstatus | Veröffentlicht - 3 Juni 2021 |
Abstract
A dominating F···π∗aromatic interaction is found to govern the benzaldehyde···tetrafluoromethane complex, as revealed by this rotational spectroscopic investigation. Secondary F···π∗-C=O- and C σ∗CF4···πaromatic interactions also contribute to the stability of the observed isomer. Narrow splittings have been observed in the rotational spectrum originating from a 3-fold internal rotation of CF4 above the aromatic moiety, and a corresponding V3 barrier was determined to be 1.572(14) kJ mol-1. This is the first rotational spectroscopic evidence in the literature implying that the aromatic π∗ antibonding orbital can be activated not only by electron-withdrawing substituents but also by complexation partners containing atoms with high electronegativity, like CF4. The results emphasize the partner molecules' role to modulate the πelectron structure and show a change in the orbital character (πor π∗) when participating in the formation of noncovalent interactions.
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in: Journal of Physical Chemistry Letters, Jahrgang 12, 03.06.2021, S. 5150-5155.
Publikation: Beitrag in Fachzeitschrift › Artikel › Forschung › Peer-Review
}
TY - JOUR
T1 - Switching Aromatic Character by Complexation
T2 - πto π∗ Change Seen in Molecular Rotation Spectra
AU - Wang, Hao
AU - Chen, Junhua
AU - Duan, Chunguo
AU - Xu, Xuefang
AU - Zheng, Yang
AU - Grabow, Jens Uwe
AU - Gou, Qian
AU - Caminati, Walther
N1 - Funding Information: We are grateful for the financial support from the National Natural Science Foundation of China (Grant No. 22073013); Fundamental Research Funds for the Central Universities (Grant No. 2020CDJXZ002); and Graduate Research and Innovation Foundation of Chongqing, China (Grant No. CYB20043).
PY - 2021/6/3
Y1 - 2021/6/3
N2 - A dominating F···π∗aromatic interaction is found to govern the benzaldehyde···tetrafluoromethane complex, as revealed by this rotational spectroscopic investigation. Secondary F···π∗-C=O- and C σ∗CF4···πaromatic interactions also contribute to the stability of the observed isomer. Narrow splittings have been observed in the rotational spectrum originating from a 3-fold internal rotation of CF4 above the aromatic moiety, and a corresponding V3 barrier was determined to be 1.572(14) kJ mol-1. This is the first rotational spectroscopic evidence in the literature implying that the aromatic π∗ antibonding orbital can be activated not only by electron-withdrawing substituents but also by complexation partners containing atoms with high electronegativity, like CF4. The results emphasize the partner molecules' role to modulate the πelectron structure and show a change in the orbital character (πor π∗) when participating in the formation of noncovalent interactions.
AB - A dominating F···π∗aromatic interaction is found to govern the benzaldehyde···tetrafluoromethane complex, as revealed by this rotational spectroscopic investigation. Secondary F···π∗-C=O- and C σ∗CF4···πaromatic interactions also contribute to the stability of the observed isomer. Narrow splittings have been observed in the rotational spectrum originating from a 3-fold internal rotation of CF4 above the aromatic moiety, and a corresponding V3 barrier was determined to be 1.572(14) kJ mol-1. This is the first rotational spectroscopic evidence in the literature implying that the aromatic π∗ antibonding orbital can be activated not only by electron-withdrawing substituents but also by complexation partners containing atoms with high electronegativity, like CF4. The results emphasize the partner molecules' role to modulate the πelectron structure and show a change in the orbital character (πor π∗) when participating in the formation of noncovalent interactions.
UR - http://www.scopus.com/inward/record.url?scp=85107711401&partnerID=8YFLogxK
U2 - 10.1021/acs.jpclett.1c01318
DO - 10.1021/acs.jpclett.1c01318
M3 - Article
C2 - 34032447
AN - SCOPUS:85107711401
VL - 12
SP - 5150
EP - 5155
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
SN - 1948-7185
ER -