Effect of bulky anions on the liquid-liquid phase transition in phosphonium ionic liquids: Ambient and high-pressure dielectric studies

Although the first-order liquid–liquid phase transition (LLT) has been reported to exist in various systems (i.e., phosphorus, silicon, water, triphenyl phosphite, etc.), it is still one of the most challenging problems in the field of physical science. Recently, we found that this phenomenon occurs in the family of trihexyl(tetradecyl)phosphonium [P 666,14 ] + based ionic liquids (ILs) with different anions (Wojnarowska et al in Nat Commun 13:1342, 2022). To understand the molecular structure–property relationships governing LLT, herein, we examine ion dynamics of two other quaternary phosphonium ILs containing long alkyl chains in cation and anion. We found that IL with the anion containing branched –O–(CH 2 ) 5 –CH 3 side chains does not reveal any signs of LLT, while IL with shorter alkyl chains in the anion brings a hidden LLT, i.e., it overlaps with the liquid-glass transition. Ambient pressure dielectric and viscosity measurements revealed a peculiar behavior of ion dynamics near T g for IL with hidden LLT. Moreover, high-pressure studies have shown that IL with hidden LLT has relatively strong pressure sensitivity compared to the one without first-order phase transition. At the same time, the former exposes the inflection point indicating the concave-convex character of logτ σ (P) dependences.