The impact of cation acidity and alkyl substituents on the cation-anion interactions of 1-alkyl-2,3-dimethylimidazolium ionic liquids.

In this study, eight 1-alkyl-2,3-dimethylimidazolium ionic liquids are analysed by X-ray photoelectron spectroscopy. The effect of both the anion and the cation on the electronic environment of cationic nitrogen regions is explored. It concludes that the cationic N 1s binding energy shifts to the lower value when the basicity of the anion increases or the acidity of the cation decreases. The impact of the cation acidity on the cation-anion interactions is demonstrated systematically by carefully comparing the binding energies of anion-based components for each anion. It is found that for more basic anions, the charge-transfer effect between counterions can be effectively shielded; for less basic anions, such an effect is negligible. The charge shielding effect of the alkyl substituent is also studied by using dodecyl-based ionic liquids, compared to 1-alkyl-3-methylimidazolium analogues. It suggests that long alkyl substituents can have a significant electron donating effect to the cation headgroup and thus effectively shield the charge-transfer effect between cations and anions.