Organic luminogens with persistent room temperature phosphorescence (RTP) have attracted great attention for their wide applications in optoelectronic devices and bioimaging. However, these materials are still very scarce, partially due to the unclear mechanism and lack of designing guidelines. Herein we develop seven 10-phenyl-10H-phenothiazine-5,5-dioxide-based derivatives, reveal their different RTP properties and underlying mechanism, and exploit their potential imaging applications. Coupled with the preliminary theoretical calculations, it is found that strong π–π interactions in solid state can promote the persistent RTP. Particularly, CS-CF3 shows the unique photo-induced phosphorescence in response to the changes in molecular packing, further confirming the key influence of the molecular packing on the RTP property. Furthermore, CS-F with its long RTP lifetime could be utilized for real-time excitation-free phosphorescent imaging in living mice. Thus, our study paves the way for the development of persistent RTP materials, in both the practical applications and the inherent mechanism.

The study of purely organic room‐temperature phosphorescence (RTP) has drawn increasing attention because of its considerable theoretical research and practical application value. Currently, organic RTP materials with both high efficiency (ΦP > 20%) and a long lifetime (τP > 10 s) in air are still scarce due to the lack of related design guidance. Here, a new strategy to increase the phosphorescence performance of organic materials by integrating the RTP host and RTP guest in one doping system to form a triplet exciplex, is reported. With these materials, the high‐contrast labeling of tumors in living mice and encrypted patterns in thermal printing are both successfully realized by taking advantage of both the long afterglow time (up to 25 min in aqueous media) and high phosphorescence efficiency (43%).

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Many luminescent stimuli responsive materials are based on fluorescence emission, while stimuli-responsive room temperature phosphorescent materials are less explored. Here, we show a kind of stimulus-responsive room temperature phosphorescence materials by the covalent linkage of phosphorescent chromophore of arylboronic acid and polymer matrix of poly(vinylalcohol). Attributed to the rigid environment offered from hydrogen bond and B-O covalent bond between arylboronic acid and poly(vinylalcohol), the yielded polymer film exhibits ultralong room temperature phosphorescence with lifetime of 2.43 s and phosphorescence quantum yield of 7.51%. Interestingly, the RTP property of this film is sensitive to the water and heat stimuli, because water could destroy the hydrogen bonds between adjacent poly(vinylalcohol) polymers, then changing the rigidity of this system. Furthermore, by introducing another two fluorescent dyes to this system, the color of afterglow with stimulus response effect could be adjusted from blue to green to orange through triplet-to-singlet Förster-resonance energy-transfer. Finally, due to the water/heat-sensitive, multicolor and completely aqueous processable feature for these three afterglow hybrids, they are successfully applied in multifunctional ink for anti-counterfeit, screen printing and fingerprint record.

We report the first example of an AIEgen (DPP-BO) with fluorescence-phosphorescence dual emission under mechanical stimulation. By carefully analyzing the crystal structure of DPP-BO, the efficient intermolecular and intramolecular interactions should account for its unique mechanoluminescence (ML) properties, especially the abnormal phosphorescence, as further confirmed by controlled experiments and theoretical calculations for the presence of ISC transitions. These results provide important information for understanding the complex ML process, possibly opening up a new way to study the inherent mechanism of ML by broadening the application of AIEgens.