2-(Indol-3-yl)- and 6-(pyrrol-2-yl)-substituted (bi)pyridine-based AIE-probes/fluorophores: synthesis and photophysical studies

Abstract

A series of new 2-(indol-3-yl)-6-(hetero)aryl substituted pyridines, 2-(indol-3-yl)-5-phenyl-substituted 2,2′-bipyridine and 5-aryl-6-(pyrrol-2-yl) substituted 2,2′-bipyridines were synthesized as push–pull fluorophores/probes by using a sequence of nucleophilic substitution reaction of hydrogen (S_NH) and inverse-demand Diels–Alder reaction. For the obtained compounds, photophysical properties were studied. All the compounds displayed ICT-activity with a large Stokes shift (up to 197 nm) and PLQY up to 0.28. Due to dual emission in polar solvents, one specific probe was able to respond to the action of the local pH changes in the microenvironment and exhibit AIE-activity. The fluorescence titration data at different pH were analyzed to estimate a pKa value of 4.50 for that specific probe. The AIE behavior was further confirmed by means of time-resolved fluorescence lifetime measurements as well as UV-vis spectroscopic studies. The correlation of the influence of the nature of substituents on the degree of ICT state was established based on the analysis of charge transfer (CT) indices and the calculated interfragment charge transfer (IFCT) values. Finally, the fluorophores reported in this study were successfully applied for cellular imaging.