Marcus Lecture Series - Technical Lecture: "Redox-active Ligand Complexes in Artificial Photosynthesis and the Reductive Side of Water Splitting"
Metal complexes with unsaturated dithiolate and iminothiolate ligands, that have been known for more than 50 years, are notable for facile one electron transfers, intense solution colors and unusual magnetic properties that defy conventional oxidation state descriptions. The bis complexes are in general square planar, including the first examples of this geometry for paramagnetic complexes and different formal dn configurations. Likewise, mixed diimine dithiolate complexes have been examined for a similar period of time and exhibit excited states that are mixtures of ligand-to-ligand and metal-to-ligand charge transfers. The Pt derivatives are solution luminescent and undergo electron transfer quenching. Recent studies of these complexes related to the light-driven generation of hydrogen from water will be described. The linking of these complexes to more strongly absorbing organic chromophores serves to increase the effectiveness of the charge transfer chromophore for hydrogen generation. In efforts, metal dithiolene complexes have been employed as catalysts, some of which will be presented.
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