Unraveling the light-activated reaction mechanism in a catalytically competent key intermediate of a multifunctional molecular catalyst for artificial photosynthesis

Zedler, Linda, Mengele, Alexander Klaus, Ziems, Karl Michael, Zhang, Ying, Wächtler, Maria, Gräfe, Stefanie, Pascher, Torbjörn, Rau, Sven, Kupfer, Stephan and Dietzek, Benjamin (2019) Unraveling the light-activated reaction mechanism in a catalytically competent key intermediate of a multifunctional molecular catalyst for artificial photosynthesis. Angewandte Chemie - International Edition, 58 (37), 13140-13148. (doi:10.1002/anie.201907247).

Abstract

Understanding photodriven multielectron reaction pathways requires the identification and spectroscopic characterization of intermediates and their excited-state dynamics, which is very challenging due to their short lifetimes. To the best of our knowledge, this manuscript reports for the first time on in situ spectroelectrochemistry as an alternative approach to study the excited-state properties of reactive intermediates of photocatalytic cycles. UV/Vis, resonance-Raman, and transient-absorption spectroscopy have been employed to characterize the catalytically competent intermediate [(tbbpy)₂Ru^II(tpphz)Rh^ICp*] of [(tbbpy)₂Ru(tpphz)Rh(Cp*)Cl]Cl(PF₆)₂ (Ru(tpphz)RhCp*), a photocatalyst for the hydrogenation of nicotinamide (NAD-analogue) and proton reduction, generated by electrochemical and chemical reduction. Electronic transitions shifting electron density from the activated catalytic center to the bridging tpphz ligand significantly reduce the catalytic activity upon visible-light irradiation.

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Contributors

Author: Karl Michael Ziems

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