Highly fluorescent triazolopyridine–thiophene D–A–D oligomers for efficient pH sensing both in solution and in the solid state

Abstract

Conjugated fluorophores have been extensively used for fluorescence sensing of various substances in the field of life processes and environmental science, due to their noninvasiveness, sensitivity, simplicity and rapidity. Most existing conjugated fluorophores exhibit excellent light-emitting performance in dilute solutions, but their properties substantially decrease or even completely vanish due to severe aggregation quenching in the solid state. Herein, we synthesize a series of triazolopyridine–thiophene donor–acceptor–donor (D–A–D) type conjugated molecules with high absolute fluorescence quantum yields (Φ_F) ranging from 80% to 89% in solution. These molecules also show unusual light-emitting properties in the solid state with Φ_F of up to 26%. We find that owing to the protonation–deprotonation process of the pyridine ring, these compounds display obvious changes in both fluorescence wavelength and intensity upon addition of acids, and these changes can be readily recovered by the successive introduction of bases. By harnessing this phenomenon, we further show that these fluorophores can be employed for efficient and reversible fluorescence sensing of hydrogen ions in a broad pH range (0.0–7.0). With the fabrication of pH testing papers and ink-printed complex patterns including butterflies and letters on substrates, we demonstrate the application of such sensors to fluorescence indication or solid state pH detection for real samples such as volatile acidic/basic gas and water-quality analysis.