The structure and hydrogen-bond behaviours of binary systems containing ionic liquid 1-butyl-3-methylimidazolium...

Mixing ionic liquids (ILs) with a molecular cosolvent can largely reduce the high viscosities, high polarities, and high costs of ILs. The macroscopic properties of IL-cosolvent mixtures have been studied extensively. However, some fundamental questions regarding the microscopic properties of the binary mixtures still remain to be answered. In this work, the structural and hydrogen-bond features of binary systems containing 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF₄]) and methanol/ethanol were studied by using the combination of Fourier-transform infrared spectroscopy (FTIR) and density functional theory (DFT) calculations. Excess infrared absorption spectroscopy with enhanced spectral resolution was used to analyse the original IR spectra. The alcohol tetramer/larger multimers, alcohol trimer, anion-alcohol, ion pair-alcohol, and ion cluster-alcohol complexes were identified in the excess spectra. With the increasing [BMIM][BF₄], the alcohol multimers gradually broke out from the larger multimers into smaller multimers. The hydrogen-bonded complex related with anion [BF₄]^- and alcohol gradually changes from anion-alcohol complex to ion pair-alcohol complex. The ion cluster-alcohol appears when the x(alcohol) is <0.50. The most stable optimized geometries of anion-alcohol, ion pair-alcohol, and ion cluster-alcohol were carefully analysed, and the hydrogen-bonds were identified. All of the hydrogen-bonds in these studied complexes had weak strength, closed shells and electrostatically dominant interactions.