TY - JOUR

T1 - Probing the n → π∗ carbonyl-carbonyl interactions in the formaldehyde-trifluoroacetone dimer by rotational spectroscopy

AU - Jin, Yan

AU - Wang, Zhen

AU - Li, Wenqin

AU - Xu, Yugao

AU - Feng, Gang

AU - Lesarri, Alberto

AU - Grabow, Jens Uwe

N1 - Funding Information: We acknowledge the National Natural Science Foundation of China (Grant No. 22273009), the Deutsche Forschungsgemeinschaft (DFG), the Land Niedersachsen, and the Spanish MICINN-FEDER (Grant No. PID2021-125015NB-I00) and FEDER-Junta de Castilla y León (Grant Nos. INFRARED IR2020-1-UVa02 and IR2021-UVa13) for financial support. Y.J. and W.L. thank the China Scholarships Council (CSC) for scholarships.

PY - 2023/3/28

Y1 - 2023/3/28

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=85150871932&partnerID=8YFLogxK

U2 - 10.1063/5.0144298

DO - 10.1063/5.0144298

M3 - Article

C2 - 37003758

AN - SCOPUS:85150871932

VL - 158

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 12

M1 - 124304

ER -