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

초록

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-d6, and that it forms a hydrogen bond with F- in DMSO-d6 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-d6 molecules. On the other hand, the global minimum Gibbs energy gas-phase complex (featuring the [F-& ctdot;HO-] H-bond) is structurally correlated with the configuration observed in DMSO-d6. 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.

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