A rotational study of the 1:1 adduct of ethanol and 1,4-dioxane

Spectrochim Acta A Mol Biomol Spectrosc. 2021 Nov 15:261:120086. doi: 10.1016/j.saa.2021.120086. Epub 2021 Jun 16.

Abstract

The pure rotational spectra of the 1:1 ethanol - 1,4-dioxane complex and its OD mono-deuterated species have been measured using pulsed-jet Fourier transform microwave spectroscopy. Conformational predictions for the plausible isomers of ethanol - 1,4-dioxane have been carried out considering the spatial orientation of gauche/trans ethanol with respect to the chair/boat and twisted conformations of 1,4-dioxane. Using Helium for the supersonic expansion, the microwave spectrum has been observed for the most stable structure. In the observed isomer, the two subunits are linked together by an OH⋯O hydrogen bond with gauche ethanol acting as proton donor to dioxane in the chair conformation. The non-covalent interactions have been characterized using different computational approaches. A small inverse Ubbelohde effect was observed after H → D isotopic substitution in the OH⋯O hydrogen bond.

Keywords: Microwave spectroscopy; Molecular adduct; Noncovalent interactions; Ubbelohde effect.

MeSH terms

  • Dioxanes*
  • Ethanol*
  • Models, Molecular
  • Molecular Conformation

Substances

  • Dioxanes
  • Ethanol
  • 1,4-dioxane