Solid‐state room‐temperature phosphorescence activated by the end‐capping strategy of cyano groups

Avoiding the tedious process of crystal cultivation and directly obtaining organic crystals with desirable phosphorescent performance is of great significance for studying their structure and properties. Herein, a set of benzophenone‐cored phosphors with bright green afterglow are obtained on a large scale through in‐situ generation via an end‐capping strategy to suppress non‐radiative triplet excitons and reinforce the intermolecular interactions. The ordered arrangement of phosphors with alkyl‐cyano groups as regulators is crucial for the enhancement of room‐temperature phosphorescence (RTP) emission, which has been further verified by the attenuated lifetimes in isolated states through the formation of inclusion complexes upon binding with pillar[5]arenes. Moreover, the hierarchical interactions of phosphors, including hydrogen bonding, π‐π stacking interactions, and van der Waals forces, are quantified by crystal structures and theoretical calculation to deeply interpret the origins of RTP emission. With this study, we provide a potential strategy for the direct acquisition of crystalline organic phosphors and modulation of RTP. Customizable benzophenone‐cored phosphors with afterglow properties were directly fabricated by a symmetrical end‐capping strategy regulated by alkyl‐cyano groups, which showed tunable phosphorescence lifetimes, quantum yields, packing mode, and intermolecular interactions. Such a robust strategy sets the basis for the construction of organic room‐temperature phosphorescence (RTP) materials and unlocks more possibilities for the designing of RTP materials with well‐defined supramolecular structures.