Organic Supramolecular Zippers with Ultralong Organic Phosphorescence by a Dexter Energy Transfer Mechanism

Ultralong organic phosphorescence (UOP) materials glow persistently in the dark, which offers new exciting possibilities in the fields of anti‐counterfeiting, photoelectric devices and biological imaging. However, the development of single‐component UOP materials remains a great challenge. Herein, we develop a single component organic supramolecular zipper system with a lifetime up to 0.77 s. Owing to the introduction of a pyrazole ring into the diphenylsulfone group, the “V” shaped molecules were artfully self‐assembled into supramolecular zippers via π–π and C−H⋅⋅⋅π interactions, that is not only of significance in highly efficient generation of triplet excitons but also facilitates a Dexter energy transfer process within supramolecular zippers, that are responsible for alleviating radiative and non‐radiative deactivation decay of triplet excitons, to finally boost the UOP. This finding not only gives a new set of guidelines for the design of single‐component UOP molecules but also reveals the UOP mechanism from a new perspective. An organic supramolecular zipper system showing fascinating ultralong organic phosphorescence (UOP) has been constructed. More importantly, detailed experimental and computational analysis suggest a new UOP mechanism involving Dexter energy transfer in single‐component materials.