The presence of the AzoDiGua in the aggregates led us to explore whether fluorescent properties could be acquired by these assemblies through the aggregation-induced fluorescence mechanism of azobenzene Using fluorescence spectroscopy, we found that the ATP/AzoDiGua aggregates displayed a broad fluorescence excitation/emission with maxima at 400 nm and 650 nm for the excitation and emission, respectively (Figures ). Notably, neither ATP nor AzoDiGua alone was significantly absorbing for a fluorescence emission at 650 nm (Figure ) nor fluorescent when excited at 400 nm (Figure , S6). Moreover, the same system prepared with ADP or AMP, instead of ATP, displayed a weak fluorescence for ADP/AzoDiGua where small aggregates formed, and no detectable signal for AMP/AzoDiGua where no assembly was observed (Figure ). All these results show that the self-assembly between ATP and AzoDiGua was instrumental in the emergence of the fluorescence from the ATP/AzoDiGua suspension. Fluorescence microscopy (Figure ) evidenced that the fluorescence emission was mainly localized at the position of the micrometer-sized ATP/AzoDiGua aggregates (Figure ), which was thus attributed to the aggregation-induced fluorescence of azobenzene within the supramolecular aggregates. Therefore, ATP and AzoDiGua self-assembled to form fluorescent aggregates while their individual components, AzoDiGua and ATP alone, were not intrinsically fluorescent in solution. We then studied how different stimuli could dynamically control the assembly and therefore affect its aggregationinduced fluorescence properties.