Effect of Imidazolium-Based Surface-Active Ionic Liquids on the Orientation of Liquid Crystals at Various...

A series of imidazolium-based surface-active ionic liquids (IM-SAILs), viz., single-chained IM-SAILs, 1-alkyl-3-methylimidazolium bromide ([C_nmim]Br, n = 12, 14, 16), 1-dodecyl-3-methylimidazolium salicylate ([C₁₂mim]Sal), 1-dodecyl-3-methylimidazolium 3-hydroxy-2-naphthoate ([C₁₂mim]HNC), 1-dodecyl-3-methylimidazolium cinnamate ([C₁₂mim]CA), 1-dodecyl-3-methylimidazolium para-hydroxy-cinnamate ([C₁₂mim]PCA), gemini IM-SAIL, and 1,2-bis(3-dodecylimidazolium-1-yl)ethane bromide ([C₁₂-2-C₁₂im]Br₂), along with three short-chained ionic liquids (ILs) [ethylammonium nitrate (EAN), propylammonium nitrate (PAN), and butylammonium nitrate (BAN)] were synthesized and applied to nematic liquid crystal (LC)/fluid interfaces. First, we evaluated the influence of the length and number of aliphatic chains as well as the counterion in the IM-SAIL structures on the anchoring of LCs at the aqueous/LC interface. It was observed that the threshold concentration of [C_nmim]Br (n = 12, 14, 16) decreased with the increase in aliphatic chain length. And double-chained [C₁₂-2-C₁₂im]Br₂ has a far lower threshold concentration than single-chained [C₁₂mim]Br. But the alteration of counterions (e.g., Br^- and aromatic counterions) scarcely affected the anchoring of LCs at the interface. Second, we investigated the alignment of LCs at the diverse IL/LC interfaces in the presence of IM-SAILs. It is found that the variations in both aliphatic chain length and number can remarkably change the trigger points of the orientational transition of LCs at the EAN/LC interface. Specifically, with a slight increase in the alkyl chain length of short-chained ILs, as the fluid medium, the orientation of LCs varied tremendously at the IL/LC interface. Therefore, the higher threshold concentration of IM-SAILs and the corresponding greater stability in the optical appearance of LCs at the EAN/LC interface compared to that of the aqueous/LC interface can be ascribed to the discrepancy in the microstructure of water and IL. Finally, we verified that the volume ratio of H₂O to EAN could more dramatically affect the alignment of LCs than the change in IM-SAIL concentration in aqueous solution. This work first illustrated the impact of SAIL structure on the LCs orientation at the aqueous/LC, IL/LC, and H₂O-IL mixture/LC interfaces, which will inspire us to obtain a stabilized molecular alignment of LCs at the IL/LC interfaces and to further design novel functionalized SAIL molecules for various chemical and biological applications.