Although persistent room‐temperature phosphorescence (RTP) emission has been observed for a few pure crystalline organic molecules, there is no consistent mechanism and no universal design strategy for organic persistent RTP (pRTP) materials. A new mechanism for pRTP is presented, based on combining the advantages of different excited‐state configurations in coupled intermolecular units, which may be applicable to a wide range of organic molecules. By following this mechanism, we have developed a successful design strategy to obtain bright pRTP by utilizing a heavy halogen atom to further increase the intersystem crossing rate of the coupled units. RTP with a remarkably long lifetime of 0.28 s and a very high quantum efficiency of 5 % was thus obtained under ambient conditions. This strategy represents an important step in the understanding of organic pRTP emission.
Persistencep ays off:B right persistentr oom-temperature phosphorescence from pure organic molecules was achieved by intermolecular electronic coupling of selected units in crystals. The combined advantages of their different excited-state configurations (i.e., the np*s tate with ah igh intersystem crossing ratea nd the pp* state with al ow radiative rate) results in ah ybrid intersystem-crossing process that leads to efficient persistent room-temperature phosphorescence.
Photoinduced organic radicals are important for chemical and physical processes of organic materials, which are extensively investigated and applied in organic synthesis, photoelectronic devices and biotechnology. However, there are rare reports of the luminescence for these photoinduced radicals, especially in the condensed state. Herein, an unexpected and interesting luminescent radical is described, which can be rapidly and reversibly generated from a simple organic crystal by gentle light irradiation in air. It was revealed that the twist and asymmetric conformation of isolated molecule in its crystal with only weak C−H⋅⋅⋅π intermolecular interactions, which led to the generation of such photoinduced luminescent radicals. In addition, dual‐channel photosensitive device with rapid response and well repeatability can be obtained based on the thin film of this organic crystal, showing both photoswitching on luminescence and conducting.
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