Nanosecond Intra-Ionic Chloride Photo-Oxidation.

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.

A quantitative model of charge injection by ruthenium chromophores connecting femtosecond to continuous irradiance conditions.

A kinetic framework for the ultrafast photophysics of tris(2,2-bipyridine)ruthenium(II) phosphonated and methyl-phosphonated derivatives is used as a basis for modeling charge injection by ruthenium dyes into a semiconductor substrate. By including the effects of light scattering, dye diffusion, and adsorption kinetics during sample preparation and the optical response of oxidized dyes, quantitative agreement with multiple transient absorption datasets is achieved on timescales spanning femtoseconds to nanoseconds. In particular, quantitative agreement with important spectroscopic handles-the decay of an excited state absorption signal component associated with charge injection in the UV region of the spectrum and the dynamical redshift of a ∼500 nm isosbestic point-validates our kinetic model. Pseudo-first-order rate coefficients for charge injection are estimated in this work, with an order of magnitude ranging from 1011 to 1012 s-1. The model makes the minimalist assumption that all excited states of a particular dye have the same charge injection coefficient, an assumption that would benefit from additional theoretical and experimental exploration. We have adapted this kinetic model to predict charge injection under continuous solar irradiation and find that as many as 68 electron transfer events per dye per second take place, significantly more than prior estimates in the literature.