Evidence for Competing Proton-Coupled Reaction Pathways of Molecular Triads in a Low-Polarity Solvent.

The temperature dependence of concerted proton-electron transfer (CPET) reactions of two anthracene-phenol-pyridine (An-PhOH-py) triads is investigated in toluene. Light excitation forms an anthracene local excited state (An), which undergoes CPET to form a charge separated state (CSS, An-PhO-pyH), which in turn undergoes CPET charge recombination (CR). In toluene, compared with polar solvents, the CSS is energetically destabilized. First, this makes another reaction competitive with CPET, which we propose is proton-coupled energy transfer (PCEnT) from An to form the short-lived excited state keto tautomer of the phenol-pyridine subunit (*[PhO═pyH]). Second, it puts CR deep into the Marcus inverted region, and CSS lifetimes therefore reach several nanoseconds at room temperature. The slow kinetics makes CR to the anthracene triplet state (An) competitive, as well as another reaction that is strongly activated and dominates CSS deactivation at ≥ 240 K for one of the triads. The latter is proposed to be CR via initial formation of the same [*PhO═PyH] state as above by an unusual electron transfer (ET) from An to pyH, instead of CR with the juxtaposed PhO. The two different pathways to form *[PhO═pyH] lead to CSS yields and lifetimes that vary significantly with temperature, and in markedly different ways between the triads. This is rationalized by the differences in the energies of the states involved. The results broaden the scope and understanding of the still rare phenomena of inverted CPET and PCEnT and may aid toward their use in solar fuels and photoredox catalysis.