N-Alkylisoquinolinium bromides and α,ω-alkanediols: Eutectic systems with co-crystal formation

This research focuses on ionic liquids (ILs), specifically N-alkylisoquinolinium bromides with various chain lengths: octyl, decyl, dodecyl, and hexadecyl. The study covers the synthesis and thermophysical characterisation of these compounds, as well as crystal structure determination for all excluding N-decylisoquinolinium bromide ([i-QuinC10][Br]). The obtained thermophysical parameters were compared with the literature data and also within the extended homologous series.The solid–liquid phase equilibria (SLE) in mixtures of ILs with certain α,ω-alkanediols (1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol) were investigated. As a result of SLE studies, eutectic mixtures capable of acting as eutectic phase-change materials - ePCMs - were determined. Additionally, a self-organization phenomenon was observed between specific pairs, leading to the formation of co-crystals (solid-complex phase). All binary mixtures with [i-QuinC8][Br] formed a simple eutectic system, while in the case of [i-QuinC10][Br], the formation of a non-congruent melting compound was observed in the systems with 1,8-octanediol and 1,10-decanediol. Among the systems with [i-QuinC12][Br], congruent melting compounds were observed for mixtures with 1,8-octanediol, 1,10-decanediol and 1,12-dodecanediol, while a simple eutectic was recorded for 1,6-hexanediol. IL [i-QuinC16][Br] co-crystalised only with 1,12-dodecanediol, while with other diols formed simple eutectic systems. Calorimetric analysis (DSC) and crystal structure determination (X-ray diffraction) were used to characterize the obtained supramolecular compounds.As a result, a series of ePCMs with melting points ranging from 295 K to 343 K are presented, with the {[i-QuinC12][Br] + 1,10-decanediol} system showing the highest enthalpy of melting (173.5 J·g−1). The found features and correlations between structure and properties imply the necessity for additional investigation, indicating the potential for a new generation of compounds with customizable physicochemical properties.