Abstract
Investigating the impact of exciton-vibration coupling (EC) of molecular aggregates on regulating the excited-state dynamics and controlling room temperature phosphorescence (RTP) emissions is crucial and challenging. We designed and synthesized ArBFO molecules and cultured two crystals with similar molecular packing and completely different luminescent mechanisms from B-form fluorescence to G-form RTP. The mechanism study combining measurement of photophysical properties, time-resolved fluorescence analysis, X-ray diffraction analysis, and theoretical calculations shows that tiny changes in molecular stacking amplify the EC value from B-form to G-form H-aggregates. The larger EC value accelerates the ISC process and suppresses the radiative singlet decay. Meanwhile, the stronger intermolecular interaction restricts non-radiative transitions. All of these facilitate green RTP emission in G-form aggregates. When treated with pressure-heating cycles, the transformation between B-form and G-form aggregates leads to a reversible blue fluorescence/green RTP switch with good reproducibility and photostability. Moreover, their potential in multi-level information encryption and anti-counterfeiting application has been well demonstrated. The results of this research deepen the understanding of the effect of aggregation on the luminescence mechanism and provide a new design guidance for developing smart materials with good performance.