Interionic bonding in aqueous phosphonium ionic liquid solutions exhibiting LCST behavior with high phase separation temperatures

Abstract

Phosphonium-derived ionic liquids have emerged as a powerful class of thermoresponsive materials with sought after Lower Critical Solution Temperature (LCST) phase separation with applications across a broad range of fields. Herein, we report the spectroscopic examination of phosphonium salts bearing the general structure [X][P_444n] wherein systematic structural variations were designed to gain a fundamental understanding behind the impact of alkyl chain length, anion size, and effective nuclear charge on their temperature-dependent phase separation behavior. Using variable temperature ¹H, ³¹P, and ¹⁹F NMR, the bonding changes which drive LCST phase separation for the assembled thermoresponsive ILs were elucidated. For the first time, spectroscopic evidence revealed a delicate balance between the interdependence of alkyl chain length and anion size on phase separation that formed the basis of new LCST design principles.