Fluoride Ion in Alcohols: Isopropanol vs Hexafluoroisopropanol.

The utility of alcohol as a hydrogen bonding donor is considered a providential avenue for moderating the high basicity and reactivity of the fluoride ion, typically used with large cations. However, the practicality of alcohol-fluoride systems in reactions is hampered by the limited understanding of the pertinent interactions between the OH group and F - . Therefore, this study comparatively investigates the thermal, structural, and physical properties of the CsF-2-propanol and CsF-1,1,1,3,3,3-hexafluoro-2-propanol systems to explicate the effects of the fluoroalkyl group on the interaction of alcohols and F - . The two systems exhibit vastly different phase diagrams despite the similar saturated concentrations. A combination of spectroscopic analyses, alcohol activity coefficient measurements, and theoretical calculations reveal the fluorinated alcohol system harbors the stronger OH···F - interactions between the two systems. The diffusion coefficient and ionic conductivity measurements attribute the present results to disparate states of ion association in the two systems.