Three S₀/S₁Conical Intersections Control Electron-Transfer-Catalyzed Chemiluminescence of 1,2-Dioxetanedione

Chemiluminescence (CL) utilizing four-membered cyclic peroxides is one of the most useful analytical techniques. Up to now, the CL mechanisms for nonketone (1,2-dioxetanes) and monoketone (1,2-dioxetanones) derivatives of four-membered cyclic peroxides have been intensively studied experimentally and theoretically in the past several decades, but no general mechanism has been concluded to rationalize the origin of high-efficiency singlet chemiexcitation. In contrast, as the only diketone derivative of four-membered cyclic peroxide, the electron-transfer (ET)-catalyzed CL of 1,2-dioxetanedione (DDO), which is most suggested as a critical step in the well-known peroxyoxalate CL (POCL), has never been theoretically investigated and uncovered yet. In this work, we theoretically investigated the rubrene-catalyzed decomposition of DDO for the first time, with a hybrid quantum mechanical/molecular mechanical model and nonadiabatic molecular dynamics simulation. The computation shows a stepwise ET-catalyzed decomposition and three S0/S1 conical intersection (CI)-controlled singlet chemiexcitation. The three universal S0/S1 CIs play different roles in the high-efficiency singlet chemiexcitation in ET-catalyzed CL of DDO and should be the true origin of the high-efficiency singlet CL. We believe that the current work could not only provide a further understanding for high-efficiency singlet CL but also provide some general clues to designed new high-efficient CL systems.