Impact of Size and Electronegativity of Halide Anions on Hydrogen Bonds and Properties of 1-Ethyl-3-methylimidazolium-Based Ionic Liquids.

The effect of the anion size and electronegativity of halide-based anions (Cl, Br, I, and BF) on the interionic interaction in 1-ethyl-3-methylimidazolium-based ionic liquids (ILs) Cmim X (X = Cl, Br, I, and BF) is studied by a combined approach of experiments (Raman, IR, UV-vis spectroscopy) and quantum chemical calculations. The fingerprint region of the Raman spectra of these Cmim X ion-pairs provides evidence of the presence of the conformational isomerism in the alkyl chain of the Cmim cation. The Raman and IR bands of the imidazolium C-H stretch vibration for Cmim X (X = Cl, Br, I, and BF) were noticeably blue-shifted with the systematic change in size of anions and the electronegativity. The observed blue shift in the C-H stretch vibration follows the order Cmim BF > Cmim I > Cmim Br > Cmim Cl, which essentially indicates the strong hydrogen bonding in the Cmim Cl ion-pair. DFT calculations predict at least four configurations for the cation-anion interaction. On the basis of relative optimized energies and basis-set-superposition-error (BSSE) corrected binding energies for all ion-pair configurations, the most active site for the anion interaction was found at the CH position of the cation. Besides information about the CH position, our DFT results give insights into the anion interaction with the ethyl and methyl chain of the cation, which was also confirmed experimentally [ Chem. Commun. 2015 , 51 , 3193 ]. The anion interaction at the CH site of the cation favors a planar geometry in Cmim X for X = Cl, Br, and I; however, for BF, the system prefers a nonplanar geometry where the anion is located over the imidazolium ring. TD-DFT results were used to analyze the observed UV-vis absorption spectra in a more adequate way giving insights into the electronic structure of the ILs. Overall, a reasonable correlation between the observed and the DFT-predicted results is established.