Relating the Induced Free Charge Density Gradient in a Room-Temperature Ionic Liquid to Molecular-Scale Organization

We report on dilution-dependent changes in the local environments of chromophores incorporated into room-temperature ionic liquid (RTIL)-molecular solvent binary systems where the ionic liquid cation and molecular solvent possess the same alkyl chain length. We have used the RTIL 1-decyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (DMPyrr⁺TFSI^-) and the molecular solvent 1-decanol. Perylene was used as a non-polar probe, and cresyl violet (CV⁺) was used as a polar probe chromophore. We observe that in both regions there is a change in the chromophore local environments with increasing 1-decanol content. The changes in the nonpolar regions of the binary RTIL-molecular solvent system occur at a lower 1-decanol concentration than changes in the polar regions. Both chromophores reorient as oblate rotors in this binary system, allowing detailed information on the relative values of the Cartesian components of the rotational diffusion constants to be extracted from the experimental data. The induced free charge density gradient, ρ_f, known to exist in RTILs, persists to high 1-decanol content (1-decanol mole fraction of 0.75), with the structural details of the gradient being reflected in depth-dependent changes in the Cartesian components of the rotational diffusion constants of CV⁺. This is the first time that changes in molecular organization have been correlated with ρ_f.