Donor‐Acceptor‐Based Conjugated Fluorescent Probes for Volatile Acid Detection

Abstract

AbstractStimuli‐responsive materials based on π‐conjugated donor‐acceptor systems have great potential for sensing applications in solution and solid state. The photophysical properties of an oligo(p‐phenylenevinylene) series consisting of five push‐pull type molecules were systematically investigated to switch their absorption and emission properties by using trifluoroacetic acid as a specific external analyte. During the trifluoracetic acid sensing, the terminal pyridine units of the molecules undergo the protonation and lead to the broader absorption band at a longer wavelength region owing to the π‐π* characteristics of molecules. Upon exposing solid samples to the trifluoracetic acid vapors, the initial color of solid samples changed from yellow to orange for three‐ring system‐based molecules and brick red to wine red color for five‐ring system‐based molecules with the shifting of emission band to the longer wavelength region. Furthermore, exposing the trifluoracetic acid‐fumed solid samples to triethylamine vapors, the color of the solid samples reverted to their original colors and emission properties. The DFT analysis indicated a decreased energy band gap for the protonated molecules compared to the neutral molecules, suggesting a redshift in both the absorption and emission spectra of the protonated molecules. Thus, all the molecules of an Oligo(p‐phenylenevinylene) series can be utilized effectively for volatile acid detection.