How to Control Excited‐State Prototropism of Photoacids via the Acidity of Ionic Liquids

Abstract

To control presence of ionic species in excited state of a fluorophore is quite challenging task. Herein, we report the unusual excited‐state prototropism of an important photoacid carbazole dissolved in water in presence of small amount of added ionic liquids (ILs). We have observed that the excited state prototropic equillibria of carbazole dissolved in water can be affected by the presence of small amount of added ILs. More importantly, the excited‐state prototropism of carbazole can be controlled via the acidity of added ILs. More specifically, we found that the fluorescence emission from the neutral prototropic form of carbazole can be observed even under highly basic conditions (aqueous NaOH, pH 12.6) in presence of only small amount of any of the added ILs such as 1‐butyl‐3‐methyl imidazolium tetrafluoroborate ([bmim][BF4]), 1‐butyl‐1‐methylpyrrolidinium bis(trifluromethansulphonyl)imide ([bmpyrr][Tf2N]) and 1‐butyl‐3‐methyl imidazolium hexafluorophosphate ([bmim][PF6]). The observed fluorescence emission from the neutral form of carbazole can be attributed to excited state protonation of carbazole anion by taking proton from IL cation. In a true sense, the excited state carbazole does not transfer the proton; rather takes the proton from IL cation. The observed unusual excited state protonation of carbazole anion to neutral carbazole, in the excited state even in highly basic conditions can be attributed to the presence of acidic protons with the IL cations. Herein, we reports quite unusual results where the IL assisted excited state protonation of carbazole anion occured in an exclusive manner in which proton from the IL cation exclusively protonate carbazole anion surrounded by highly alkaline media (water, pH 12.6). ILs acidity controlled excited‐state properties of important photoacids can have a wide range of chemical and biological applications and the observed results can play important roles in chemical technology to control prototropic equillibra with the help of ILs for some specific application. These observations can open new windows to attract more applications for these alternative solvent media to applications in pH and pOH jump experiments, effective photo protecting agents and chemical lasers.