RT info:eu-repo/semantics/article
T1 Interaction topologies of the S⋯O chalcogen bond: the conformational equilibrium of the cyclohexanol⋯SO2 cluster
A1 Jin, Yan
A1 Saragi, Rizalina Tama
A1 Juanes San José, Marcos
A1 Feng, Gang
A1 Lesarri Gómez, Alberto Eugenio
K1 Cyclohexanol
K1 Ciclohexanol
K1 Sulfur dioxide
K1 Dióxido de azufre
K1 Chalcogens
K1 Calcógenos
K1 Intermolecular forces
K1 Fuerzas intermoleculares
AB The conformational landscape of the cyclohexanol⋯SO2 cluster was revealed in the gas phase using chirped-pulsed broadband rotational spectroscopy and quantum chemical calculations. Four isomers stabilized by a dominant S⋯O chalcogen bond and cooperative C–H⋯O[double bond, length as m-dash]S and O–H⋯O[double bond, length as m-dash]S secondary weak hydrogen bonds were observed, with a near-parallel orientation of the S[double bond, length as m-dash]O and O–H bonds. Isomers formed by equatorial-gauche cyclohexanol are more stable than the isomers containing axial cyclohexanol. The multiple conformations of cyclohexanol and the versatile binding properties of SO2, simultaneously operating as nucleophile and electrophile through its π-holes and non-bonding electrons lead to a complex conformational behavior when the cluster is formed. The long (2.64–2.85 Å) attractive S⋯O interaction between SO2 and cyclohexanol is mainly electrostatic and the contribution of charge transfer is obvious, with an NBO analysis suggesting that the strength of the S⋯O interaction is nearly two orders of magnitude larger than the hydrogen bonds. This study provides molecular insights into the structural and energetic characteristics that determine the formation of pre-nucleation clusters between SO2 and a volatile organic compound like cyclohexanol.
PB Royal Society of Chemistry
SN 1463-9084
YR 2021
FD 2021
LK https://uvadoc.uva.es/handle/10324/47818
UL https://uvadoc.uva.es/handle/10324/47818
LA eng
NO Physical Chemistry Chemical Physics, 2021, vol. 23,  n. 18; p. 10799-10806
NO Producción Científica
DS UVaDOC
RD 27-dic-2024