Investigating the effect of systematically modifying the molar ratio of hydrogen bond donor and acceptor on solvation characteristics of deep eutectic solvents formed using choline chloride salt and polyalcohols

Abstract

Choline chloride-based deep eutectic solvents (DESs) are immensely popular in organic synthesis, catalysis, electrochemistry, and separation science. A popular choice of hydrogen bond donor (HBD) among these DESs consists of both straight-chain and branched polyols that can incorporate additional functional groups, such as ether linkages. Previous studies have shown that the extraction efficiency is significantly altered when the molar ratio of HBD in choline chloride-based DES systems is varied, but no study has been able to relate it to their solvation characteristics. This is largely due to the limited sensitivity of existing solvatochromic dye techniques to detect minor changes in solvation interactions when the DES composition is varied. In this study, inverse gas chromatography was employed for the first time to investigate the variation in solvation properties for DESs comprised of choline salts as hydrogen bond acceptors (HBAs) and polyols as HBDs when their HBA/HBD ratio is systematically altered. Unlike many organic solvents, DES systems investigated in this work possessed a significant hydrogen bond character. It was observed that the hydrogen bond basicity generally plateaued at higher molar ratios of HBD while the hydrogen bond acidity was observed to be the highest at HBA/HBD ratios of 1:10 in all DESs. Amongst all solvents, neat HBDs (triethylene glycol and 1,8-octane diol) possessed the weakest hydrogen bond basicity since they lack the chloride anion that acts as the primary hydrogen bond acceptor. Results from this study demonstrate that the solvation characteristics of DESs are largely different from their starting materials while the HBA/HBD ratio further influences their solvation interactions that can in turn impact important parameters such as extraction yields.

Keywords: Catalysis; Eutectic mixtures; Extractions; Green solvents; Organic synthesis; Separations; Solvation interactions; Sustainable chemistry.