Excited State Molecular Dynamics of Photoinduced Proton-Coupled Electron Transfer in Anthracene-Phenol-Pyridine Triads

Photoinduced proton-coupled electron transfer (PCET) in anthracene-phenol-pyridine triads exhibits inverted region behavior, where the more thermodynamically favorable process is slower. The long-lived transient charge-separated state (CSS) associated with electron transfer from phenol to anthracene and inverted region behavior were only observed experimentally for certain triads. Herein, excited state molecular dynamics simulations were performed on four different triads to simulate the nonequilibrium dynamics following photoexcitation to the locally excited state (LES) of anthracene. These simulations identified two distinct PCET pathways: the triads exhibiting inverted region behavior transitioned from the LES to the CSS, whereas the other triads transitioned to a local electron-proton transfer (LEPT) state within phenol and pyridine. The simulations suggest that PCET to the LEPT state is slower than PCET to the CSS and provides an alternative relaxation pathway. The mechanistic pathways, as well as the time scales of the electron and proton transfers, can be controlled by tuning the substituents.