Characterizing the Magnitude and Structure-Dependence of Free Charge Density Gradients in Room-Temperature Ionic...

We have reported previously on the existence of charge-induced long-range organization in the room-temperature ionic liquid (RTIL), BMIM⁺BF₄^-. The induced organization is in the form of a free charge density gradient (ρ_f) that exists over ca. 100 μm into the RTIL in contact with a charged surface. The fluorescence anisotropy decay of a trace-level charged chromophore in the RTIL is measured as a function of distance from the indium-doped tin oxide support surface to probe this free charge density gradient. We report here on the characterization of the free charge density gradient in five different imidazolium RTILs and use these data to evaluate the magnitude of the induced free charge density gradient. Both the extent and magnitude of this gradient depend on the chemical structures of the cationic and anionic constituents of the RTIL used. Control over the magnitude of ρ_f has implications for the utility of RTILs for a host of applications that remain to be explored fully.