Controllable Ultralong Phosphorescence through Substituent Modulation for Dynamic Anti‐Counterfeiting

Abstract The development of highly stable and ultra‐long organic room temperature phosphorescence (RTP) materials holds great promise for applications in anti‐counterfeiting and information protection. To improve the encryption level, the exploration of organic materials with tunable phosphorescence and afterglow features is in urgent need. Hereby, a series of long‐lived organic systems with RTP is developed by incorporating benzocarbazole derivatives into a polyvinyl alcohol (PVA) matrix (BCz@PVA). Notably, the BCz@PVA film exhibits outstanding RTP behavior with an ultralong phosphorescence lifetime (τ_p) of 2.09 s, high phosphorescence quantum yield (Φ_p) of 46.335%, and an ultra‐long afterglow duration of 15 s. Moreover, the BCz@PVA film maintains excellent RTP performance even after being placed in ambient conditions for 60 days. Theoretical calculations reveal that the excellent RTP performance of BCz@PVA film is attributed to the stronger intermolecular interactions, the smaller energy gap (ΔE_st) between the singlet and triplet states, and stable molecular stacking mode. Furthermore, color‐tunable photoluminescence (PL), distinct τ_p, and afterglow duration are successfully achieved by adjusting the position of the Br substituent on the benzene ring. Based on their diverse RTP performances and excellent stability, the corresponding BCz@PVA film provides successful application for multi‐level high‐security anti‐counterfeiting and information protection.