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Mesoionic carbenes have found wide use as components of homogeneous catalysts. Recent discoveries have, however, shown that metal complexes of such ligands also have huge potential in photochemical research and in the activation of small molecules. We present here three Re complexes with mesoionic pyridyl-carbene ligands. The complexes display reduction steps which were investigated via UV-vis-NIR-IR spectro-electrochemistry, and these results point toward an EC mechanism. The Re compounds emit in the visible range in solution at room temperature with excited state lifetimes that are dependent on the substituents of the mesoionic carbenes. These complexes are also potent electrocatalysts for the selective reduction of CO to CO. Whereas the substituents on the carbenes have no influence on the reduction potentials, the electrocatalytic efficiency is strongly dependent on the substituents. This fact is likely a result of catalyst instability. The results presented here thus introduce mesoionic carbenes as new potent ligands for the generation of emissive Re complexes and for electrocatalytic CO reduction.
This article was published in the following journal.
Name: Inorganic chemistry
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Rhenium. A metal, atomic number 75, atomic weight 186.2, symbol Re. (Dorland, 28th ed)
OXADIAZOLES bearing an oxygen at the 5-position. They are mesoionic, with delocalized positive and negative charges.
Chemical reactions effected by light.
Complexes containing CHLOROPHYLL and other photosensitive molecules. They serve to capture energy in the form of PHOTONS are generally found as components of the PHOTOSYSTEM I PROTEIN COMPLEX or the PHOTOSYSTEM II PROTEIN COMPLEX.
Compounds that accept electrons in an oxidation-reduction reaction. The reaction is induced by or accelerated by exposure to electromagnetic radiation in the spectrum of visible or ultraviolet light.