Aggregation Behavior of Long-Chain N-Aryl Imidazolium Bromide in Aqueous Solution

The aggregation behavior of three long-chain N-aryl imidazolium ionic liquids (ILs), 1-(2,4,6-trimethylphenyl)-3-alkylimidazolium bromide [Cnpim]Br (n = 10, 12, and 14), in aqueous solutions was systematically explored by surface tension, electrical conductivity, and 1H NMR. A lower critical micelle concentration (cmc) for the N-aryl imidazolium ILs is observed compared with that for 1,3-dialkylimidazolium ILs [Cnmim]Br, indicating that the incorporation of the 2,4,6-trimethylphenyl group into a headgroup favors micellization. The enhanced π−π interactions among the adjacent 2,4,6-trimethylphenyl groups weaken the steric hindrance of headgroups and thus lead to a dense arrangement of [Cnpim]Br molecules at the air−water interface. An analysis of the 1H NMR spectra revealed that the introduced 2,4,6-trimethylphenyl group may slightly bend into the hydrophobic regions upon micellization. The micelle formation process for [Cnpim]Br (n = 10, 12, and 14) was found to be enthalpy-driven in the investigated temperature range, which is attributed to the strong electrostatic self-repulsion of the headgroups and the counterions as well as the π−π interactions among headgroups. Strong, stable fluorescence properties are presented by the new N-aryl imidazolium ILs, indicating their potential application in the field of photochemistry.