Rigidly Locked Pyrene Excimers in Planar Chiral Pyrenophanes for Intense and Stable Circularly Polarized Photoluminescence and Electrochemiluminescence

Aiming at the construction of novel platforms with excellent performances in both circularly polarized photoluminescence (CP‐PL) and electrochemiluminescence (CP‐ECL), a new family of pyrenophanes with rigidly locked pyrene dimers and varied bridges has been designed and synthesized. Attributed to densely packed pyrene excimers, the resultant pyrenophanes revealed tunable bridge‐dependent emission behaviors, as investigated by femtosecond time‐resolved transient absorption spectroscopy. More importantly, all these planar chiral pyrenophanes display strong CP‐PL with large dissymmetry factor (gPL) values up to 0.034, and such excellent performances remain stable in a wide range of solvents, temperatures, and concentrations. Attractively, the highest gECL values up to 0.014 reported so far has been achieved for the CP‐ECL emissions of the chiral pyrenophanes. Attributed to their unique structural features and outstanding CPL performances, these novel pyrenophanes could serve as promising platforms for both fundamental investigations on pyrene excimers and practical applications such as chiral sensing.