The influence of hydrophilicity on the orientational dynamics and structures of imidazolium-based ionic liquid/water binary mixtures.

The orientational dynamics and microscopic structures of imidazolium-based ionic liquids of varying hydrophilicity were investigated using optical heterodyne-detected optical Kerr effect (OHD-OKE) spectroscopy and atomistic simulations. Hydrophilicity was tuned via anion selection, cation alkyl chain length, and the addition of a strong hydrogen bond donor on the cation (protic ionic liquid). In the hydrophobic samples, which saturate at relatively low water concentration, OHD-OKE data display Debye Stokes Einstein (DSE) behavior as a function of water concentration. The DSE behavior indicates that the microstructures of the hydrophobic ionic liquid/water mixtures do not fundamentally change as a function of water concentration. The hydrophilic samples have two regimes of different DSE behaviors demonstrating the presence of two structural regimes depending on water concentration. These experimental results indicate that in hydrophilic ionic liquid/water samples, significant structural changes occur to accommodate high water concentrations, while hydrophobic samples become water saturated because the restructuring of local ionic structures is unfavorable. Atomistic simulations show that the local ionic microstructures experience distinct changes in these hydrophilic ionic liquid/water binary samples because of the delicate interplay of intermolecular interactions among imidazolium cations, hydrophilic anions, and water molecules.