Leveraging Coupled Solvatofluorochromism and Fluorescence Quenching in Nitrophenyl‐Containing Thiazolothiazoles for Efficient Organic Vapor Sensing
Andrew R. Brotherton, Abhishek Shibu, Jared C. Meadows, Nickolas A. Sayresmith, Chloe E. Brown, Ana Montoya Ledezma, Thomas A. Schmedake, Michael G. Walter
Abstract
Abstract Solvatofluorochromic molecules provide strikingly high fluorescent outputs to monitor a wide range of biological, environmental, or materials‐related sensing processes. Here, thiazolo[5,4‐d]thiazole (TTz) fluorophores equipped with simple alkylamino and nitrophenyl substituents for solid‐state, high‐performance chemo‐responsive sensing applications are reported. Nitroaromatic substituents are known to strongly quench dye fluorescence, however, the TTz core subtly modulates intramolecular charge transfer (ICT) enabling strong, locally excited‐state fluorescence in non‐polar conditions. In polar media, a planar ICT excited‐state shows near complete quenching, enabling a twisted excited‐state emission to be observed. These unique fluorescent properties (spectral shifts of 0.13 – 0.87 eV and large transition dipole moments Δ µ = 20.4 – 21.3 D) are leveraged to develop highly sought‐after chemo‐responsive, organic vapor optical sensors. The sensors are developed by embedding the TTz fluorophores within a poly(styrene‐isoprene‐styrene) block copolymer to form fluorescent dye/polymer composites ( Φ F = 70 – 97%). The composites respond reversibly to a comprehensive list of organic solvents and show low vapor concentration sensing (e.g., 0.04% solvent saturation vapor pressure of THF – 66 ppm). The composite films can distinguish between solvent vapors with near complete fluorescent quenching observed when exposed to their saturated solvent vapor pressures, making this an extremely promising material for optical chemo‐responsive sensing.