Details
| Translated title of the contribution | Gestapelt, nicht geklebt: Enthüllung der π→π*-Wechselwirkung mithilfe des Benzofuran-Formaldehyd-Komplexes |
|---|---|
| Original language | English |
| Article number | e202113737 |
| Journal | Angewandte Chemie - International Edition |
| Volume | 61 |
| Issue number | 1 |
| Early online date | 25 Oct 2021 |
| Publication status | Published - 27 Dec 2021 |
Abstract
The 1:1 benzofuran–formaldehyde complex has been chosen as model system for analyzing π→π* interactions in supramolecular organizations involving heteroaromatic rings and carbonyl groups. A joint “rotational spectroscopy–quantum chemistry” strategy unveiled the dominant role of π→π* interactions in tuning the intermolecular interactions of such adduct. The exploration of the intermolecular potential energy surface led to the identification of 14 low-energy minima, with 4 stacked isomers being more stable than those linked by hydrogen bond or lone-pair→π interactions. All energy minima are separated by loose transition states, thus suggesting an effective relaxation to the global minimum under the experimental conditions. This expectation has been confirmed by the experimental detection of only one species, which was unambiguously assigned owing to the computation of accurate spectroscopic parameters and the characterization of 11 isotopologues. The large number of isotopic species opened the way to the determination of the first semi-experimental equilibrium structure for a molecular complex of such a dimension.
Keywords
- bond analysis, non-covalent interaction, quantum chemistry, rotational spectroscopy, structure determination
ASJC Scopus subject areas
- Chemical Engineering(all)
- Catalysis
- Chemistry(all)
- General Chemistry
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In: Angewandte Chemie - International Edition, Vol. 61, No. 1, e202113737, 27.12.2021.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Stacked but not Stuck
T2 - Unveiling the Role of π→π* Interactions with the Help of the Benzofuran–Formaldehyde Complex
AU - Li, Xiaolong
AU - Spada, Lorenzo
AU - Alessandrini, Silvia
AU - Zheng, Yang
AU - Lengsfeld, Kevin Gregor
AU - Grabow, Jens Uwe
AU - Feng, Gang
AU - Puzzarini, Cristina
AU - Barone, Vincenzo
N1 - Funding Information: Financial support from the Italian Ministry of University and Research (Grant Number 2017A4XRCA), the Chongqing University, the Land Niedersachsen, and the Deutsche Forschungsgemeinschaft (DFG) are acknowledged. X. Li thanks the China Scholarships Council (CSC) for support. K. G. Lengsfeld gratefully acknowledges the Fonds der Chemischen Industrie (FCI) for a Ph.D. fellowship. Open Access Funding provided by Scuola Normale Superiore within the CRUI‐CARE Agreement.
PY - 2021/12/27
Y1 - 2021/12/27
N2 - The 1:1 benzofuran–formaldehyde complex has been chosen as model system for analyzing π→π* interactions in supramolecular organizations involving heteroaromatic rings and carbonyl groups. A joint “rotational spectroscopy–quantum chemistry” strategy unveiled the dominant role of π→π* interactions in tuning the intermolecular interactions of such adduct. The exploration of the intermolecular potential energy surface led to the identification of 14 low-energy minima, with 4 stacked isomers being more stable than those linked by hydrogen bond or lone-pair→π interactions. All energy minima are separated by loose transition states, thus suggesting an effective relaxation to the global minimum under the experimental conditions. This expectation has been confirmed by the experimental detection of only one species, which was unambiguously assigned owing to the computation of accurate spectroscopic parameters and the characterization of 11 isotopologues. The large number of isotopic species opened the way to the determination of the first semi-experimental equilibrium structure for a molecular complex of such a dimension.
AB - The 1:1 benzofuran–formaldehyde complex has been chosen as model system for analyzing π→π* interactions in supramolecular organizations involving heteroaromatic rings and carbonyl groups. A joint “rotational spectroscopy–quantum chemistry” strategy unveiled the dominant role of π→π* interactions in tuning the intermolecular interactions of such adduct. The exploration of the intermolecular potential energy surface led to the identification of 14 low-energy minima, with 4 stacked isomers being more stable than those linked by hydrogen bond or lone-pair→π interactions. All energy minima are separated by loose transition states, thus suggesting an effective relaxation to the global minimum under the experimental conditions. This expectation has been confirmed by the experimental detection of only one species, which was unambiguously assigned owing to the computation of accurate spectroscopic parameters and the characterization of 11 isotopologues. The large number of isotopic species opened the way to the determination of the first semi-experimental equilibrium structure for a molecular complex of such a dimension.
KW - bond analysis
KW - non-covalent interaction
KW - quantum chemistry
KW - rotational spectroscopy
KW - structure determination
UR - http://www.scopus.com/inward/record.url?scp=85119669512&partnerID=8YFLogxK
U2 - 10.1002/anie.202113737
DO - 10.1002/anie.202113737
M3 - Article
AN - SCOPUS:85119669512
VL - 61
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
SN - 1433-7851
IS - 1
M1 - e202113737
ER -