Hydrogen-Bonding-Mediated Molecular Vibrational Suppression for Enhancing the Fluorescence Quantum Yield Applicable for Visual Phenol Detection

It is generally accepted that while efficient suppression of molecular vibration is inevitable for purely organic phosphors due to their long emission lifetime in the regime of 1 ms or longer, fluorophores having a lifetime in the nanoseconds regime are not sensitive to collisional quenching. Here, however, we demonstrate that a fluorophore, 2,S-bis(hexyloxy)-terephthaldehyde (BHTA), capable of having hydrogen bonding (H bonding) via its two aldehyde groups can have a largely enhanced (450%) fluorescence quantum yield (QY) in amorphous poly(acrylic acid) (PAA) matrix compared to its crystalline powder. We ascribe this enhanced QY to the efficient suppression of molecular vibrations via intermolecular H bonding. We confirm this feasibility by conducting temperature-dependent fluorescence emission intensity measurement. As gaseous phenol can intervene with the H bonding between BHTA and PAA, interestingly, BHTA embedded in PAA can selectively detect gaseous phenol by a sharp fluorescence emission intensity drop that is visibly recognizable by the naked eye. The results provide an insightful molecular design strategy for a fluorophore and fluorometric sensory system design for enhanced photoluminescence QY and convenient detection of various volatile organic compounds.