Light-induced charge separation in ruthenium based triads – New variations on an old theme

Success with artificial photosynthesis requires control of the photoinduced electron transfer reactions leading to charge-separated states. In this review, some new ideas to optimize such charge-separated states in ruthenium(II) polypyridyl based three-component systems with respect to: (1) long lifetimes and (2) ability to store sufficient energy for catalytic water splitting, are presented. To form long-lived charge-separated states, a manganese complex as electron donor and potential catalyst for water oxidation has been used. The recombination reaction is unusually slow because it occurs deep down in the Marcus normal region as a consequence of the large bond reorganization following the manganese oxidation. For the creation of high energy charge-separated states, a strategy using bichromophoric systems is presented. By consecutive excitations of the two chromophores, the formation of charge-separated states that lie higher in energy than either of the two excited states could in theory be achieved, the first results of which will be discussed in this review.

Light induced charge separation in a Ru(bpy)3-based triad with a Mn2-donor unit shows an extraordinary long lifetime of around 1 s in 140 K butyronitrile. In a different, bichromophoric triad we attempted to generate a charge-separated state with a very high energy by the successive absorption of two photons.Figure optionsDownload as PowerPoint slide