Details
| Original language | English |
|---|---|
| Pages (from-to) | 8874-8879 |
| Number of pages | 6 |
| Journal | The journal of physical chemistry letters |
| Volume | 14 |
| Issue number | 39 |
| Early online date | 27 Sept 2023 |
| Publication status | Published - 5 Oct 2023 |
Abstract
This study reports the observation and characterization of two isomers of the acrolein dimer by using high-resolution rotational spectroscopy in pulsed jets. The first isomer is stabilized by two hydrogen bonds, adopting a planar configuration, and is energetically favored over the second isomer, which exhibits a dominant n → π* interaction in a nearly orthogonal arrangement. Surprisingly, the n → π* interaction was revealed to enable a concerted tunneling motion of two moieties along the carbonyl group. This motion leads to the inversion of transient chirality associated with the exchange of donor-acceptor roles, as revealed by the spectral feature of quadruplets. Inversion of transient chirality is a fundamental phenomenon in quantum mechanics and commonly observed for only inversional motions of protons. It is the first discovery, to the best of our knowledge, that such heavy moieties can also undergo chirality inversion.
ASJC Scopus subject areas
- Materials Science(all)
- General Materials Science
- Chemistry(all)
- Physical and Theoretical Chemistry
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In: The journal of physical chemistry letters, Vol. 14, No. 39, 05.10.2023, p. 8874-8879.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - n → π* Interaction Enabling Transient Inversion of Chirality
AU - Wang, Hao
AU - Caminati, Walther
AU - Li, Meng
AU - Chen, Junhua
AU - Tian, Xiao
AU - Grabow, Jens Uwe
AU - Gou, Qian
N1 - Funding Information: The authors are grateful for support from the National Natural Science Foundation of China (Grant22073013), Chongqing Talents: Exceptional Young Talents Project(Grantcstc2021ycjh-bgzxm0027), and the Fundamental Research Funds for the Central Universities (Grant2020CDJXZ002).
PY - 2023/10/5
Y1 - 2023/10/5
N2 - This study reports the observation and characterization of two isomers of the acrolein dimer by using high-resolution rotational spectroscopy in pulsed jets. The first isomer is stabilized by two hydrogen bonds, adopting a planar configuration, and is energetically favored over the second isomer, which exhibits a dominant n → π* interaction in a nearly orthogonal arrangement. Surprisingly, the n → π* interaction was revealed to enable a concerted tunneling motion of two moieties along the carbonyl group. This motion leads to the inversion of transient chirality associated with the exchange of donor-acceptor roles, as revealed by the spectral feature of quadruplets. Inversion of transient chirality is a fundamental phenomenon in quantum mechanics and commonly observed for only inversional motions of protons. It is the first discovery, to the best of our knowledge, that such heavy moieties can also undergo chirality inversion.
AB - This study reports the observation and characterization of two isomers of the acrolein dimer by using high-resolution rotational spectroscopy in pulsed jets. The first isomer is stabilized by two hydrogen bonds, adopting a planar configuration, and is energetically favored over the second isomer, which exhibits a dominant n → π* interaction in a nearly orthogonal arrangement. Surprisingly, the n → π* interaction was revealed to enable a concerted tunneling motion of two moieties along the carbonyl group. This motion leads to the inversion of transient chirality associated with the exchange of donor-acceptor roles, as revealed by the spectral feature of quadruplets. Inversion of transient chirality is a fundamental phenomenon in quantum mechanics and commonly observed for only inversional motions of protons. It is the first discovery, to the best of our knowledge, that such heavy moieties can also undergo chirality inversion.
UR - http://www.scopus.com/inward/record.url?scp=85173570085&partnerID=8YFLogxK
U2 - 10.1021/acs.jpclett.3c02264
DO - 10.1021/acs.jpclett.3c02264
M3 - Article
C2 - 37756497
AN - SCOPUS:85173570085
VL - 14
SP - 8874
EP - 8879
JO - The journal of physical chemistry letters
JF - The journal of physical chemistry letters
SN - 1948-7185
IS - 39
ER -