Seoncheol Cha

Characteristics of Visible Fluorescence from Ionic Liquids

The observation of fluorescence in the visible spectral range in imidazolium-based ionic liquids, in which the peak of the fluorescence spectrum shifts with the change in the excitation wavelength by over 200 nm, was reported by Samanta and co-workers (Paul et al. J. Phys. Chem. B 2005, 109, 9148; Chem. Phys. Lett. 2005, 402, 375), and the aggregate structure in the bulk ionic liquid was suggested to explain this unique phenomenon. In this work, by employing 2D-scan fluorescence spectroscopy, we identified the long- and short-wavelength fluorescence components of the fluorescence spectrum of 1-butyl-3-methylimidazolium tetrafluoroborate ([C4MIM][BF4]), of which only the long-wavelength fluorescence component was found to be responsible for the reported fluorescence properties. The fluorescence intensity of the long-wavelength component decreased much faster upon dilution in aqueous mixtures than the short-wavelength component, supporting the conclusion that the long-wavelength fluorescence is from molecular aggregates in the bulk ionic liquid. Fluorescence correlation spectroscopy (FCS), which was used to accurately account for the number density of the long-wavelength fluorescent species in aqueous solutions of the ionic liquid, also suggested that the fluorescence came from aggregate structures of molecules in ionic liquids.

Raman Spectroscopic Study on Alkyl Chain Conformation in 1‐Butyl‐3‐methylimidazolium Ionic Liquids and their Aqueous Mixtures

Ionic liquids of 1-butyl-3-methylimidazolium ([BMIM]) cation with different anions (Cl- , Br- , I- , and BF4- ), and their aqueous mixtures were investigated by using Raman spectroscopy and dispersion-included density functional theory (DFT). The characteristic Raman bands at 600 and 624 cm-1 for two isomers of the butyl chain in the imidazolium cation showed significant changes in intensity for different anions as well as in aqueous solutions. The area ratio of these two bands followed the order I- >Br- >Cl- >BF4- (in terms of the anion X in [BMIM]X), indicating that the butyl chain of [BMIM]I tends to adopt the trans conformation. The butyl chain was found to adopt the gauche conformation upon dilution, irrespective of the anion type. The Raman bands in the butyl C-H stretch region for [BMIM]X (X=Cl- , Br- , and I- ) blueshifted significantly with the increase in the water concentration, whereas that for [BMIM]BF4 changed very little upon dilution. The blueshift in the C-H stretch region upon dilution also followed the order: [BMIM]I>[BMIM]Br>[BMIM]Cl>[BMIM]BF4 , the same order as the above trans conformation preference of the butyl chain in pure imidazolium ionic liquids, which suggested that the cation-anion interaction plays a role in determining the conformation of the chain.