Organic Persistent RTP Crystals: From Brittle to Flexible by Tunable Self‐Partitioned Molecular Packing

Aiming to solve the trade-off of "room-temperature phosphorescence (RTP)-flexibility" in principle, organic RTP crystals with elastic/plastic deformation are realized. These properties are mainly due to the divisional aggregation structures of aromatics and alkoxy chains, and can be modulated by the controllable molecular configurations. The longest RTP lifetime of 972.3 ms is achieved as the highest record for organic flexible crystals. Plastic crystals with persistent RTP are realized, which can be applied into biomedical optical technologies by afterglow delivery. Moreover, the relationship among elastic/plastic deformation, RTP property, and aggregated structures is established. The elastic/plastic deformation is mainly determined by the difference of interaction energies from the aromatics and the alkoxy chains. For the BP-OR series with twisted configurations, the alkoxy chain with the middle length is favorable for the RTP property, while the strength of the π-π coupling is the cruical factor to the RTP property of the Xan-OR series with planar skeletons. A new way to promote the development of flexible RTP crystals, by modulation of aggregated structures as well as rational distribution of intermolecular interactions, is explored.