Metal-free organic phosphorescence materials are of imperious demands in optoelectronics and bioelectronics. However, it is still a formidable challenge to develop a material with simultaneous efficiency and lifetime enhancement under ambient conditions. In this study, we design and synthesize a new class of high efficient ultralong organic phosphorescence (UOP) materials through self-assembly of melamine and aromatic acids in aqueous media. A supramolecular framework can be formed via multiple intermolecular interactions, building a rigid environment to lock the molecules firmly in a three-dimensional network, which not only effectively limits the nonradiative decay of the triplet excitons but also promotes the intersystem crossing. Thus, the supermolecules we designed synchronously achieve an ultralong emission lifetime of up to 1.91 s and a high phosphorescence quantum efficiency of 24.3% under ambient conditions. To the best of our knowledge, this is the best performance of UOP materials with simultaneous efficiency and lifetime enhancement. Furthermore, it is successfully applied in a barcode identification in darkness. This result not only paves the way toward high efficient UOP materials but also expands their applications.

Visible light is much more available and less harmful than ultraviolet light, but ultralong organic phosphorescence (UOP) with visible-light excitation remains a formidable challenge. Here, a concise chemical approach is provided to obtain bright UOP by tuning the molecular packing in the solid state under irradiation of available visible light, e.g., a cell phone flashlight under ambient conditions (room temperature and in air). The excitation spectra exhibit an obvious redshift via the incorporation of halogen atoms to tune intermolecular interactions. UOP is achieved through H-aggregation to stabilize the excited triplet state, with a high phosphorescence efficiency of 8.3% and a considerably long lifetime of 0.84 s. Within a brightness of 0.32 mcd m that can be recognized by the naked eye, UOP can last for 104 s in total. Given these features, ultralong organic phosphorescent materials are used to successfully realize dual data encryption and decryption. Moreover, well-dispersed UOP nanoparticles are prepared by polymer-matrix encapsulation in an aqueous solution, and their applications in bioimaging are tentatively being studied. This result will pave the way toward expanding metal-free organic phosphorescent materials and their applications.

Efficient ultralong organic phosphorescent materials have potential applications in some fields, such as bioimaging, anti‐counterfeiting, and sensors. Nevertheless, phosphorescence efficiencies of metal‐free organic materials are low due to weak spin–orbit coupling and vigorous nonradiative transitions under ambient conditions. Here a chemical strategy to improve phosphorescence efficiency with intermolecular π‐type halogen bonding construction via isomerism is presented. X‐ray single crystal analysis reveals that different halogen bonding is formed among p‐BrTCz, m‐BrTCz, and o‐BrTCz crystals. Phosphorescence efficiency of m‐BrTCz in solid can reach 13.0%, seven times of o‐BrTCz in solid owing to effective π‐type halogen bonding, which is further confirmed by theoretical calculations. However, ultralong phosphorescence lifetimes are little affected, 155, 120, and 156 ms for p‐BrTCz, m‐BrTCz, and o‐BrTCz in the solid state, respectively. Furthermore, a simple pattern for data encryption and decryption is first demonstrated under sunlight. This result will provide an approach for improving the phosphorescent efficiency of metal‐free organic phosphors with ultralong luminescence.