We report on changes in the magnitude and length scale of the induced free charge density gradient, ρf, in three imidazolium room temperature ionic liquids (RTILs) with dilution by methanol...

The piezoelectric effect was discovered over a century ago, and it has found wide application since that time. The direct piezoelectric effect is the production of charge upon application of force to a material, and the converse piezoelectric effect is a change in the material dimension(s) upon the application of a potential. To date, piezoelectric effects have been observed only in solid-phase materials. We report here the observation of the direct piezoelectric effect in room-temperature ionic liquids (RTILs). The RTILs 1-butyl-3-methyl imidazolium bis(trifluoromethyl-sulfonyl)­imide (BMIM+TFSI–) and 1-hexyl-3-methyl imidazolium bis­(trifluoro­methyl­sulfonyl) imide (HMIM+TFSI–) produce a potential upon the application of force when confined in a cell, with the magnitude of the potential being directly proportional to the force applied. The effect is one order of magnitude smaller than that seen in quartz. This is the first report to our knowledge of the direct piezoelectric effect in a neat liquid. Its discovery has fundamental implications about the organization and dynamics in ionic liquids and invites theoretical treatment.

Room temperature ionic liquids (RTILs) have a wide range of current and potential applications, in areas ranging from supercapacitor energy storage to sequestration of toxic gas phase species and use as reusable solvents for selected organic reactions. All these applications stem from their unique physical and chemical properties, which remain understood to only a limited extent. Among the issues of greatest importance is the extent to which RTILs exist as dissociated ionic species and the length scales over which some types of organizations are seen to exist in them. In this Invited Feature Article, we review the current understanding of organization in this family of materials, where opportunities lie in terms of deepening our understanding, and what potential applications would benefit from gaining such knowledge.

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We report on dilution-dependent changes in the local environments of chromophores incorporated into roomtemperature 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-1methylpyrrolidinium 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 (1decanol 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 .