Conformations of, and Non-covalent Interactions in, binary fluoroalcohol∙∙∙1,4-dioxane aggregates: Rotational Spectroscopic and DFT studies

  • Author / Creator
    Yang, Qian
  • Conformations of, and non-covalent interactions in, binary aggregates of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) and 1-phenyl-2,2,2-trilfuoroethanol (PhTFE) with 1,4-dioxane were investigated. These fluoroalcohols and 1,4-dioxane are common solvents for organic reactions. Rotational spectra of the two fluorinated alcohols and 1,4-dioxane mixtures were measured in a supersonic expansion using a chirped-pulse and a cavity-based Fourier transform microwave spectrometers. Systematic conformational searches were carried out using CREST, a recently developed conformational searching tool by Grimme and co-workers, and the subsequent DFT calculations were used to predict the rotational spectroscopic constants and electric dipole components, as well as relative energies to aid the spectral assignments. One conformer of the HFIP∙∙∙1,4 dioxane and two conformers of the PhTFE∙∙∙1,4 dioxane dimer were identified experimentally. The non-covalent interactions involved were further analyzed and visualized using the quantum theory of atoms in molecules (QTAIM), non-covalent interactions (NCI) and symmetric-adapted perturbation theory (SAPT) approaches. New insights into the roles of intra- and intermolecular interactions in the conformational relative stability of the above hydrogen-bonded complexes were extracted based on the experimental and theoretical results. Overall, these studies provide important contributions to understanding how 1,4-dioxane affects the conformational spaces of the fluoroalcohol binding partners.

  • Subjects / Keywords
  • Graduation date
    Fall 2022
  • Type of Item
  • Degree
    Master of Science
  • DOI
  • License
    This thesis is made available by the University of Alberta Library with permission of the copyright owner solely for non-commercial purposes. This thesis, or any portion thereof, may not otherwise be copied or reproduced without the written consent of the copyright owner, except to the extent permitted by Canadian copyright law.