NMR investigation of imidazolium-based ionic liquids and their aqueous mixtures

1H and 13C NMR spectroscopy is employed to investigate the interaction of water with two imidazolium-based ionic liquids (ILs), 1-hexyl-3-methylimidazolium bromide ([C 6mim]Br) and 1-octyl-3-methylimidazolium bromide ([C 8mim]Br), at IL concentrations well above the critical aggregation concentration (CAC). The results are compared with those of the neat samples. To this aim, a detailed analysis of the changes in the 1H chemical shifts, 13C relaxation parameters, and 2D ROESY data due to the presence of water is performed. The results for both neat ILs are consistent with a packed structure where head-to-head, head-to-tail, and tail-to-tail contacts occur and where the site of maximal mobility restriction is at the polar head. At the lowest investigated water content, the presence of water influences mainly the environment around the IL polar head, slowing down the motional dynamics of the aromatic ring with respect to the alkyl chain. At higher water contents this difference diminishes, the motional freedom of the whole molecule increasing. The presence of ROESY cross-peaks between protons in the polar and apolar IL regions, as well as between protons in non-neighboring alkyl groups, at all investigated water contents suggests that the alkyl tails are not fully segregated in hydrophobic domains, as expected for micelle-like structures. Holding water: The interaction of water with the ionic liquids (ILs) 1-hexyl- and 1-octyl-3-methylimidazolium bromide, at IL concentrations above the critical aggregation concentration, is investigated by NMR spectroscopy (see figure). Water influences the environment close to the polar region of ILs at the lowest water content. Upon increasing the water fraction, the IL molecules form aggregates where contacts occur between the polar and apolar regions. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.