Inflection Point in Pressure Dependence of Ionic Conductivity as a Fingerprint of Local Structure Formation.

In this study, we employed dielectric spectroscopy to investigate the effect of temperature and pressure on the ion dynamics of phosphonium ionic liquids (ILs) differing by the length of an alkyl chain, [P666, n ][TFSI] ( n = 2, 6, 8, 12). We found that both temperature and pressure dependence of dc-conductivity (σdc ) determined for all examined ILs herein exhibit unique characteristics, unusual for aprotic ILs. Two regions differing by ion self-organization have been identified from the derivative analysis of σdc ( T -1 ) data. On the other hand, isothermal measurements performed at elevated pressure revealed a unique concave-convex character of σdc ( P ) dependences, resulting in a clear minimum in the pressure behavior of activation volume. Such an inflection point characterizing the pressure dependence of σdc in [P666, n ][TFSI] ILs can be considered an inherent feature of ion dynamics governed by structural self-assembly. Our results offer a unique perspective to link the ion mobility at various T - P conditions to the nanostructural organization of ionic systems.