Isomer and substituent engineering of TADF emitters toward tunable room-temperature phosphorescence

Metal-free organic phosphorescent materials are crucial for the advancement of optoelectronics and bioelectronics. Nonetheless, achieving rational control over the performance of room-temperature phosphorescence (RTP) presents a significant challenge. In this study, two sets of isomeric thermally activated delayed fluorescence (TADF) emitters with a donor–acceptor (D-A) configuration are designed and synthesized. Their RTP efficiency and lifetime are regulated by tuning their energy levels and molecular packing modes through isomer and substituent engineering. All of these materials exhibited afterglow emission, with the exception of 4-CzAIPh. A comprehensive investigation was conducted on the packing modes in the crystalline state, which revealed that the three RTP materials possess strong π-π interactions and numerous intermolecular forces, providing stability to the long-lived triplet excitons of RTP. Especially, 4-CzAIAd demonstrated the fastest intersystem crossing rate, the smallest fractional free volume and relatively larger spin–orbit coupling between its singlet and triplet states, as well as between its triplet state and ground state, which explains its longest phosphorescence lifetime of 301 ms.