Effect of lithium salt on fluorescence quenching in glycerol: a comparison with ionic liquid/deep eutectic solvent

Abstract

It was reported earlier that the addition of LiCl to the deep eutectic solvent (DES) ChCl:Urea (composed of the salt choline chloride and the H-bond donor urea in 1 : 2 molar ratio) and the addition of LiTf₂N [Tf₂N:(CF₃SO₂)₂N] to the ionic liquid (IL) [C₂C₁im][Tf₂N] ([C₂C₁im]:1-ethyl-3-methylimidazolium), respectively, results in an increase in the dynamic viscosity of the medium. However, as the concentration of the Li salt is increased, instead of decreasing, the bimolecular quenching rate constant (k_q) for the quenching of pyrene fluorescence by nitromethane is observed to first increase and only then decreases within both media. This unusual initial increase in quenching is hypothesized to be due to structural changes in the DES ChCl:Urea and the IL [C₂C₁im][Tf₂N], respectively, as the Li salt is added. We tested this hypothesis by comparing the physical properties and fluorescence quenching behavior between 1 wt% water in glycerol solution which has similar viscosity to that of the DES ChCl:Urea with the aforementioned DES and IL in the presence of lithium salt as media. In complete contrast, irrespective of the temperature, k_q is found to decrease monotonically with increasing concentration of LiCl within 1 wt% water in glycerol media. These findings therefore highlight the unusual characteristics of ILs and DESs as solubilizing media. The ionic nature of the IL and the high concentration of ions in the DES are deemed responsible for these outcomes.