Layered structure of room-temperature ionic liquids in microemulsions by multinuclear NMR spectroscopic studies

Abstract

Microemulsions form in mixtures of polar, nonpolar, and amphiphilic molecules. Typical microemulsions employ water as the polar phase. However, microemulsions can form with a polar phase other than water, which hold promise to diversify the range of properties, and hence utility, of microemulsions. Here microemulsions formed by using a room-temperature ionic liquid (RTIL) as the polar phase were created and characterized by using multinuclear NMR spectroscopy. 1H, 11B, and 19F NMR spectroscopy was applied to explore differences between microemulsions formed by using 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]) as the polar phase with a cationic surfactant, benzylhexadecyldimethylammonium chloride (BHDC), and a nonionic surfactant, Triton X-100 (TX-100). NMR spectroscopy showed distinct differences in the behavior of the RTIL as the charge of the surfactant head group varies in the different microemulsion environments. Minor changes in the chemical shifts were observed for [bmim]+ and [BF 4]- in the presence of TX-100 suggesting that the surfactant and the ionic liquid are separated in the microemulsion. The large changes in spectroscopic parameters observed are consistent with microstructure formation with layering of [bmim]+ and [BF4]- and migration of Cl- within the BHDC microemulsions. Comparisons with NMR results for related ionic compounds in organic and aqueous environments as well as literature studies assisted the development of a simple organizational model for these microstructures. Confining ions: Multinuclear NMR experiments were used to explore two different reverse micelle systems formed by using a cationic and nonionic surfactant with the room-temperature ionic liquid (RTIL) [bmim][BF4] (bmim=1-butyl-3-methylimidazolium) as the polar phase. Microemulsions formed by using a cationic surfactant revealed layering of the RTIL that does not occur in systems formed with the nonionic surfactant (see figure).