Understanding the Microscopic Behavior of Binary Mixtures of Ionic Liquids Through Various Spectroscopic Techniques.

In recent times it has been shown that certain binary mixture of pure ionic liquids having appropriate chemical composition can behave like a new chemical entity. However, current knowledge about the microscopic behavior of these interesting systems is rather limited. The present study is undertaken with an objective to understand the microscopic behavior in terms of intermolecular interaction, structure and dynamics of these systems. In the present study, few (IL+IL) mixtures are chosen with a common cation and a variation of anion. The investigations are also carried out by taking individual pure ILs so that the difference in behavior between pure IL and (IL+IL) mixtures are understood. Initially the systems have been investigated by studying the thermophysical properties of the concerned mixtures. Synergistic effect between combining pure ILs through photochromism has also been studied. These mixtures have been investigated further through steady state and time resolved fluorescence spectroscopy, electron paramagnetic resonance (EPR), nuclear magnetic resonance (NMR) and fluorescence correlation spectroscopy (FCS). Interestingly, time-resolved fluorescence data also pointed out that (IL+IL) mixtures are not only spatially heterogeneous but they are dynamically heterogeneous too. EPR measurements have suggested that the micro-polarity (ET(30)) of (IL+IL) mixture is close to aliphatic polyalcohols. Measurements of translational diffusion coefficients of the diffusing species through NMR and FCS studies have provided idea about the nano-structural organization within (IL+IL) binary mixtures. The analysis of data essentially reveals that the mixtures of ILs that are used in the current study do not behave like a non-ideal solution. The behavior of the IL mixtures is observed to be more like quasi-ideal type.