Rhenium Complexes of Pyridyl-Mesoionic Carbenes: Photochemical Properties and Electrocatalytic CO2 Reduction.
2020
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 ReI 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 ReI 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 CO2 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 ReI complexes and for electrocatalytic CO2 reduction.
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