Dual-State Emissive and Substituent-Tunable pH-Sensitive Bis-Heterocyclic Fluorescent Probes

Abstract

A library of fluorescent molecules based on imidazopyridine linked with benzothiazole and benzimidazole was assessed for pH sensitivity and the effect of substituents thereon, also leading to dual-state emission. A broad range of pH (1–13) was evaluated, where the benzothiazole-based (BnTA) compounds responded in acidic pH, whereas the benzimidazole-based (BnIm) compounds behaved differently at different pH with recognizable color change on shifting from acidic to neutral and then to basic. NMR titrations revealed the effect of substituents on governing the site of protonation and deprotonation. Further, the mechanism of fluorescence was comprehended through theoretical calculations. On assessing the solid state fluorescence briefly, 2e showed mechanochromic behavior, showing green fluorescence in the solid state, which vanished upon grinding, and upon fuming with acetone, the fluorescence turned yellowish orange, which reverted to the initial fluorescence upon long-term exposure of acetone. The cellular uptake and fluorescence response of 2l in pH were also evaluated. The colocalization experiment suggested that 2l crossed the nuclear membrane and stained the nucleus, showing its possible in vitro application. The compound serves as a potential lead for other applications likewise, such as optoelectronics, data encryption, and pH sensors.