Molecular Assembling in Mixtures of Hydrophilic 1-Butyl-1-Methylpyrrolidinium Dicyanamide Ionic Liquid and Water

The infrared absorbance spectrum of the ionic liquid 1-butyl-1-methylpyrrolidinium dicyanamide, mixed with water at two different concentrations, was measured between 160 and 300 K in the mid infrared range. Both mixtures do not crystallize on cooling; however, remarkably, the one with an ionic liquid (IL):water composition of 1:3 displays a cold crystallization process on heating in a restricted temperature range between 240 and 250 K. A portion of the water participates to the cold crystallization. On the contrary, with an IL:water composition of 1:6.6 no crystallization takes place. Upon water addition the vibration frequencies of the anion and of some lines of the cation are blue shifted, while the absorption lines of water are red shifted. These facts are interpreted as the evidence of the occurrence of the hydrogen bonding of water, as the hydrogen bonding acceptor with respect to the anion (anion center dot center dot center dot O-H bonds develop) and as hydrogen donor for the cation (C-H center dot center dot center dot O bonds can form). Microscopic inhomogeneities in the samples and their evolution with temperature are discussed.