Ultrafast Hydrogen Bond Exchanging between Water and Anions in Concentrated Ionic Liquid Aqueous Solutions

The mixtures of 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM]BF₄) ionic liquids (ILs) and water as a function of IL concentrations have been investigated by Fourier transform infrared (FTIR) spectroscopy and ultrafast two-dimensional IR (2D IR) spectroscopy. FTIR spectra of the mixtures resolve two different types of water species, one interacting with the BF₄^- anions and the other associated with bulklike water molecules. These two water species are in a dynamic equilibrium through forming different hydrogen bonding configurations which are separated by more than 100 cm^-1 in the IR spectra. The structural dynamics of the IL mixtures are further revealed by monitoring the vibrational relaxation dynamics of the OD stretching group of interfacial water molecules hydrogen bonded to BF₄^- anions. With the increase of the IL bulk concentration, vibrational population and rotational dynamics of the interfacial water molecules can be described by a biexponential decay function and are strongly dependent on the IL concentrations. Furthermore, the ultrafast hydrogen bond exchanging between water and BF₄^- anions in the ILs are also measured using 2D IR spectroscopy. The average hydrogen bond exchanging rate is determined to be 19 ± 4 ps, which is around 3 times slower than that in the NaBF₄ electrolyte aqueous solution. The much slower hydrogen bond exchanging rate indicates that the local structure of ILs and water molecules are strongly mediated by the steric effect of the cationic group in the ILs, which is proposed to be responsible for the formation of the heterogeneous structure in the IL mixtures. By using SCN^- as the anionic probe, the structural inhomogeneity in the IL solutions can be confirmed from the distinct rotational dynamics of the SCN^-, which is segregated from the rotational dynamics of water molecules in the IL mixtures.