High-Field EPR Spectroscopic Characterization of Spin Probes in Aqueous Ionic Liquid Mixtures

Binary mixtures of the hydrophilic room temperature ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim⁺][BF₄ ^-]) and water have been probed using high-field/high-frequency electron paramagnetic resonance (EPR) spectroscopy. By adding nitroxide radicals as paramagnetic tracers, the solution structure could be assessed from typical solutes' points of view. Three probe molecules, differing in charge and hydrogen bonding affinity, have been employed: the dianionic Fremy's salt, amphiphilic TEMPO, and hydrophilic TEMPOL. High-field pulse EPR spectroscopy has been used to determine hyperfine interaction tensors and g-matrices under cryogenic conditions. Polarity-proticity plots reveal the interaction of the nitroxide moiety with apolar (TEMPO) and ionic (FS) nano-domains, depending on the probe structure. Only small variations are observed on changing the water content suggesting that the probes are well shielded from aqueous subdomains. The results indicate that addition of water in fact stabilizes IL-rich mesostructures by embedding them in pools of water.