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Pure organic emitting materials with room-temperature phosphorescence (RTP), showing large Stokes shifts with long emitting lifetime, low preparation cost, good processability, and wide applications in analysis, bioimaging, organic light emitting diode, and so forth, have been drawing great attentions recently. Related to the design strategy for metal-free RTP materials, the phosphors containing heavy atoms (Br, I, etc.) and other heteroatoms (O, S, etc.) to facilitate the singlet-to-triplet intersystem crossing (ISC) to populate the triplet are usually employed. Besides this factor, the pathways of nonradiative relaxation are inhibited as much as possible. Crystalline packing was the commonly used strategy to engender the rigid environment to suppress the nonradiative decay, and thus to enhance the RTP emission. However, crystal RTP materials might usually be provided with not good enough repeatability and processability, which would restrict their specific practical applications special for biosystem. Instead, amorphous metal-free RTP materials could overcome such deficiencies. Recently, great efforts have been devoted to develop challengeable amorphous metal-free materials and expand their potential applications. This Account mainly focuses on the recent progress on amorphous pure organic RTP system, focusing on the rigid effect to restrict the nonradiative decay to induce or enhance the RTP emission via supramolecular interactions such as host-guest interaction and hydrogen-bonding rigid matrix. Typical host-guest assembling and supramolecular polymer systems, hydrogen-binding copolymers, and small molecules for RTP emission, as well as the heavy-atom free assembling systems for RTP emission are well illustrated in this Account. In the summary, we also give some future perspectives and research direction of the area of pure organic RTP systems, such as enhancement of emission quantum yield, emission color tuning, possible device applications, and the remaining challenge. Moreover, based on these amorphous RTP material examples and beyond, we herein would like to conclude and propose a new concept as "Assembling-Induced Emission", the key thought of which systems is "control molecular motions, then control emission" via supramolecular dynamic assembling. This assembling-induced emission strategy is applicable in many emissive assembling systems besides such amorphous RTP materials introduced in this Account. We hope this concept will be a helpful guide for understanding the emissive mechanism and constructing strategy of various emissive materials.
Ma et al. (Thu,) studied this question.