Probing the hydroxyl in [2,2,2]-cryptand/KF/choline chloride non-covalent host–guest complex in solution by ¹⁹F-NMR spectroscopy: structural correlation and thermodynamic reversal of host–guest configurations in solution and in the gas pha

We study the structures of the [2,2,2]-cryptand/KF/choline chloride ([2,2,2]/KF/ChCl) non-covalent host-guest complex in solution using ¹⁹F-NMR spectroscopy. We examine the environment around the hydroxyl group in the ChCl guest, to determine whether the functional group forms a hydrogen bond with the [2,2,2]/KF host or interacts with solvent molecules (dimethyl sulfoxide (DMSO), ethylene glycol (EG)). We find that the ¹⁹F peaks are characteristic of the structural features of the complex, showing that the -OH group in the ChCl guest is solvated away from the [2,2,2]/KF host in EG-<i>d</i>₆, and that it forms a hydrogen bond with F^- in DMSO-<i>d</i>₆ isolated from the solvent. By carrying out density functional theory (DFT) calculations, we find that a gas-phase [2,2,2]/KF/Ch⁺ conformer (with a 'naked' -OH group) of higher Gibbs free energy (by 13.6 kcal mol^-1) is structurally connected to the solution-phase configuration, where the -OH forms H-bonds with EG-<i>d</i>₆ molecules. On the other hand, the global minimum Gibbs energy gas-phase complex (featuring the [F^-⋯HO-] H-bond) is structurally correlated with the configuration observed in DMSO-<i>d</i>₆. These observations of 'thermodynamic reversal' and structural correlation of the [2,2,2]/KF/ChCl complexes in the two phases, connected by the electrospray ionization/mass spectroscopy (ESI/MS) procedure, are discussed in relation to the potential for explicating host-guest-solvent interactions in solution from gas-phase host-guest configurations.