Comparison of the Performance of Fluorescent, Phosphorescent, and TADF Luminophores for Explosives Sensing

ABSTRACT This study investigates how the emission mechanism (fluorescence, phosphorescence, or thermally activated delayed fluorescence, TADF) of a luminescence‐quenching chemical sensor influences the sensitivity of explosives detection. Steady‐state and time‐resolved photoluminescence measurements were used to evaluate the quenching kinetics of representative emitters in the presence of 2,4‐dinitrotoluene ( DNT ), a model nitroaromatic explosive. Linear Stern‐Volmer behavior was observed for the fluorescent and phosphorescent emitters, whereas the TADF compound exhibited a pronounced downward deviation in steady‐state measurements, arising from the simultaneous but distinct quenching of singlet and triplet exciton populations. To describe this behavior, we derived a modified Stern–Volmer formalism comprising separate relationships for the prompt and delayed fluorescence. The quenching dynamics of the TADF system were found to be strongly dependent on the intrinsic parameters , k Stot and k Ttot , with the singlet and triplet populations being quenched with different efficiencies. These insights highlight the potential of TADF luminophores to act as sensitive photoinduced electron transfer‐based explosives sensors.