Probing the Microscopic Aspects of 1-Butyl-3-Methylimidazolium Trifluoroacetate Ionic Liquid and Its Mixture with Water and Methanol: A Photophysical and Theoretical (DFT) Study

Considering the potential of mixed ionic liquid-cosolvent systems in wide range of applications, photophysical and theoretical studies on an industrially important ionic liquid, 1-butyl-3-methylimidazolium trifluoroacetate (BMIMTFA), and also its mixture with water and methanol have been investigated. Two organic dipolar solutes coumarin 153 (C153) and 2-aminonitrofluorene (ANF) have been used as the probe molecule for the present study. Steady-state absorption and emission spectral behavior of C153 has not been significantly influenced by both the cosolvents. However, excitation wavelength dependent measurements with ANF in the BMIMTFA-water and BMIMTFA-methanol show entirely different photophysical response. For BMIMTFA-methanol system the average solvation and rotational time is found to be less than that in BMIMTFA-water system. Quite interestingly, time-resolved fluorescence anisotropy measurements reveal two different solute-solvent coupling constant (C _obs ) even if same mole fraction of water and methanol is used for the mixed solvent systems. Theoretical calculations also reveal stronger intermolecular interaction between IL and methanol than that between IL and water. The present combined photophysical and theoretical calculations seem to suggest different microscopic structural organization in the two binary systems.