Anti-Kasha’s Rule Emissive Switching Induced by Intermolecular H-Bonding

The exploration of emission pathways from high-excited states in organic luminogens has recently become prosperous owing to improved possibilities to study so-called anti-Kasha’s rule emission with the potential of improving the luminescent quantum efficiency. However, emission pathway switching among different high-excited states has rarely been addressed through external control. We here present a rational design and synthesis of a novel azulene-based emitter to achieve a responsive control of its anti-Kasha’s rule emissive switching. The emitter initially gives rise to an S3-to-S0 dominant emission as indicated by our experimental and theoretical studies. On this basis, it can be toggled into an S2-to-S0 dominant emission upon the H-bond formation between the triformyl groups and water molecules. Such a process, which originates from the H-bonding regulated distribution of excited-state energy, is accompanied by a remarkable fluorescent color conversion and a significant improvement of the fluorescent quantum yield in the azulene family. Moreover, a reversible emissive switching in doped films was observed to depend on a solid-state H-bond tuning process with moisture sensitivity. These results may provide new insight for building advanced chemical systems for visualized sensing with high distinguishability.