Substituent Effects on Photochemistry of Anthracene–Phenol–Pyridine Triads Revealed by Multireference Calculations

Inverted region behavior for concerted proton-coupled electron transfer (PCET) was recently demonstrated for biomimetic anthracene–phenol–pyridine molecular triads. Photoexcitation of the anthracene to a locally excited state (LES) is followed by concerted electron transfer from the phenol to the anthracene and proton transfer from the phenol to the pyridine, forming a relatively long-lived charge separated state (CSS). The long-lived CSS and the inverted region behavior associated with the decay from the CSS to the ground state through charge recombination were experimentally observed only for triads with certain substituents on the anthracene and the pyridine. To explain this distinction, we computed the proton potential energy curves in four substituted triads using the complete active space self-consistent-field method and multireference perturbation theory, including solvent effects with a dielectric continuum model. The calculations revealed a local electron–proton transfer (LEPT) state, in which both the electron and proton transfer from the phenol to the pyridine. When the LEPT state is lower in energy than the CSS, it may provide an alternative pathway for fast decay from the LES to the ground state and thereby preclude detection of the CSS and the inverted region behavior. These calculations predict that substituents stabilizing negative charge on the pyridine and destabilizing negative charge on the anthracene will favor the LEPT pathway, while substituents with the reverse effects will favor the CSS pathway, which could exhibit inverted region behavior. These insights about the stabilization of energy-storing charge-separated states have implications for designing and controlling PCET reactions in artificial photosynthetic systems and other energy conversion processes.