The non-covalent bonding features of carbonyl–carbonyl interactions have been investigated in the dimer of formaldehyde and trifluoroacetone using high resolution rotational spectroscopy combined with quantum chemical calculations. The observation of all possible isotopic substitutions for the heavy atoms in the complex enabled the determination of the accurate structure, characterized by the antiparallel arrangement of the two C=O bonds. The two moieties are connected through a dominant n → π* interaction enhanced by one weak C–H⋯O hydrogen bond, as revealed by supporting natural bond orbital analysis and symmetry-adapted perturbation theory analysis. Further computational investigations on 17 related adducts stabilized by carbonyl–carbonyl n → π* interactions show how the interaction strength is regulated by the incorporation of either electron-donating or withdrawing functional groups.
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28 March 2023
Research Article|
March 22 2023
Probing the n → π* carbonyl–carbonyl interactions in the formaldehyde–trifluoroacetone dimer by rotational spectroscopy
Yan Jin
;
Yan Jin
(Formal analysis, Investigation, Writing – review & editing)
1
School of Chemistry and Chemical Engineering, Chongqing University
, Daxuecheng South Rd. 55, 401331 Chongqing, China
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Zhen Wang
;
Zhen Wang
(Formal analysis, Investigation, Writing – original draft, Writing – review & editing)
1
School of Chemistry and Chemical Engineering, Chongqing University
, Daxuecheng South Rd. 55, 401331 Chongqing, China
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Wenqin Li;
Wenqin Li
(Investigation, Writing – review & editing)
2
Departamento de Química Física y Química Inorgánica, Facultad de Ciencias—I.U. CINQUIMA, Universidad de Valladolid
, Paseo de Belén 7, 47011 Valladolid, Spain
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Yugao Xu;
Yugao Xu
(Investigation, Writing – review & editing)
1
School of Chemistry and Chemical Engineering, Chongqing University
, Daxuecheng South Rd. 55, 401331 Chongqing, China
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Gang Feng
;
Gang Feng
a)
(Conceptualization, Formal analysis, Funding acquisition, Methodology, Project administration, Supervision, Writing – original draft, Writing – review & editing)
1
School of Chemistry and Chemical Engineering, Chongqing University
, Daxuecheng South Rd. 55, 401331 Chongqing, China
a)Authors to whom correspondence should be addressed: fengg@cqu.edu.cn; alberto.lesarri@uva.es; and jens-uwe.grabow@pci.uni-hannover.de
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Alberto Lesarri
;
Alberto Lesarri
a)
(Conceptualization, Funding acquisition, Methodology, Project administration, Resources, Supervision, Writing – original draft, Writing – review & editing)
2
Departamento de Química Física y Química Inorgánica, Facultad de Ciencias—I.U. CINQUIMA, Universidad de Valladolid
, Paseo de Belén 7, 47011 Valladolid, Spain
a)Authors to whom correspondence should be addressed: fengg@cqu.edu.cn; alberto.lesarri@uva.es; and jens-uwe.grabow@pci.uni-hannover.de
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Jens-Uwe Grabow
Jens-Uwe Grabow
a)
(Conceptualization, Funding acquisition, Methodology, Project administration, Resources, Supervision, Writing – original draft, Writing – review & editing)
3
Institut für Physikalische Chemie and Elektrochemie, Gottfried Wilhelm Leibniz Universität Hannover
, Callinstraße 3A, 30167 Hannover, Germany
a)Authors to whom correspondence should be addressed: fengg@cqu.edu.cn; alberto.lesarri@uva.es; and jens-uwe.grabow@pci.uni-hannover.de
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a)Authors to whom correspondence should be addressed: fengg@cqu.edu.cn; alberto.lesarri@uva.es; and jens-uwe.grabow@pci.uni-hannover.de
J. Chem. Phys. 158, 124304 (2023)
Article history
Received:
January 29 2023
Accepted:
March 03 2023
Citation
Yan Jin, Zhen Wang, Wenqin Li, Yugao Xu, Gang Feng, Alberto Lesarri, Jens-Uwe Grabow; Probing the n → π* carbonyl–carbonyl interactions in the formaldehyde–trifluoroacetone dimer by rotational spectroscopy. J. Chem. Phys. 28 March 2023; 158 (12): 124304. https://doi.org/10.1063/5.0144298
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