Abstract: Transition-metal photocatalysts capable of oxidizing chloride are rare yet serve as an attractive means to controllably generate chlorine atoms, which have continued to garner the interest of researchers for notable applications in photoredox catalysis and solar energy storage. Herein, a new series of four Ir-photocatalysts with different dicationic chloride-sequestering ligands were synthesized and characterized to probe the relationship between chloride binding affinities, ion pair solution structures, and rate constants for chloride photo-oxidation in acetonitrile at room temperature. The substituents on the quaternary amines of dicationic bipyridine ligands had negligible effects on the photocatalyst excited-state reduction potential, yet dramatically influenced the affinity for chloride binding, indicating that synthetic design can be utilized to independently tune these important properties. An inverse correlation was observed between the equilibrium constant for chloride ion pairing and the rate constant for intra-ionic chloride oxidation. Exceptions to this trend suggest structural differences in the ion-paired solution structures, which were probed by 1H NMR binding experiments. This study provides new insights into light-induced oxidation of ion-paired substrates, a burgeoning approach that offers to circumvent diffusional constraints of photocatalysts with short excited-state lifetimes. Ground-state association of chloride with these photocatalysts enables intra-ionic chloride oxidation on a rapid nanosecond timescale.
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