Triplet quenching pathway control with molecular dyads enables the identification of a highly oxidizing annihilator class.

Metal complex - arene dyads typically act as more potent triplet energy donors compared to their parent metal complexes, which is frequently exploited for increasing the efficiencies of energy transfer applications. Using unexplored dicationic phosphonium-bridged ladder stilbenes (P-X) as quenchers, we exclusively observed photoinduced electron transfer photochemistry with commercial organic photosensitizers and photoactive metal complexes. In contrast, the corresponding pyrene dyads of the tested ruthenium complexes with the very same metal complex units efficiently sensitize the P-X triplets. The long-lived and comparatively redox-inert pyrene donor triplet in the dyads thus provides an efficient access to acceptor triplet states that are otherwise very tricky to obtain. This dyad-enabled control over the quenching pathway allowed us to explore the P-X photochemistry in detail using laser flash photolysis. The P-X triplet undergoes annihilation producing the corresponding excited singlet, which is an extremely strong oxidant (+2.3 V NHE) as demonstrated by halide quenching experiments. This behavior was observed for three P derivatives allowing us to add a novel basic structure to the very limited number of annihilators for sensitized triplet-triplet annihilation in neat water.