Unraveling the Light-Activated Reaction Mechanism in a Catalytically Competent Key Intermediate of a Multifunctional Molecular Catalyst for Artificial Photosynthesis

Zedler L, Mengele AK, Ziems KM, Zhang Y, Waechtler M, Gräfe S, Pascher T, Rau S, Kupfer S, Dietzek B (2019)

Publication Type: Journal article

Publication year: 2019

Journal

Angewandte Chemie International Edition Wiley

Book Volume: 58

Pages Range: 13140-13148

Journal Issue: 37

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)2RuII(tpphz)RhICp*] 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.

Involved external institutions

Leibniz-Institut für Photonische Technologien e.V. DE Germany (DE) Universität Ulm DE Germany (DE) Friedrich-Schiller-Universität Jena DE Germany (DE) Pascher Instruments AB SE Sweden (SE)

How to cite

APA:

Zedler, L., Mengele, A.K., Ziems, K.M., Zhang, Y., Waechtler, M., Gräfe, S.,... Dietzek, B. (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. https://doi.org/10.1002/anie.201907247

MLA:

Zedler, Linda, et al. "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 (2019): 13140-13148.

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