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

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...

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Autores principales: Zedler, Linda, Mengele, Alexander Klaus, Ziems, Karl Michael, Zhang, Ying, Wächtler, Maria, Gräfe, Stefanie, Pascher, Torbjörn, Rau, Sven, Kupfer, Stephan, Dietzek, Benjamin
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2019
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6772164/
https://www.ncbi.nlm.nih.gov/pubmed/31347251
http://dx.doi.org/10.1002/anie.201907247
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author Zedler, Linda
Mengele, Alexander Klaus
Ziems, Karl Michael
Zhang, Ying
Wächtler, Maria
Gräfe, Stefanie
Pascher, Torbjörn
Rau, Sven
Kupfer, Stephan
Dietzek, Benjamin
author_facet Zedler, Linda
Mengele, Alexander Klaus
Ziems, Karl Michael
Zhang, Ying
Wächtler, Maria
Gräfe, Stefanie
Pascher, Torbjörn
Rau, Sven
Kupfer, Stephan
Dietzek, Benjamin
author_sort Zedler, Linda
collection PubMed
description 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)(2)Ru(II)(tpphz)Rh(I)Cp*] of [(tbbpy)(2)Ru(tpphz)Rh(Cp*)Cl]Cl(PF(6))(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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spelling pubmed-67721642019-10-07 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 Dietzek, Benjamin Angew Chem Int Ed Engl Research Articles 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)(2)Ru(II)(tpphz)Rh(I)Cp*] of [(tbbpy)(2)Ru(tpphz)Rh(Cp*)Cl]Cl(PF(6))(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. John Wiley and Sons Inc. 2019-08-19 2019-09-09 /pmc/articles/PMC6772164/ /pubmed/31347251 http://dx.doi.org/10.1002/anie.201907247 Text en © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc-nd/4.0/ License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non‐commercial and no modifications or adaptations are made.
spellingShingle Research Articles
Zedler, Linda
Mengele, Alexander Klaus
Ziems, Karl Michael
Zhang, Ying
Wächtler, Maria
Gräfe, Stefanie
Pascher, Torbjörn
Rau, Sven
Kupfer, Stephan
Dietzek, Benjamin
Unraveling the Light‐Activated Reaction Mechanism in a Catalytically Competent Key Intermediate of a Multifunctional Molecular Catalyst for Artificial Photosynthesis
title Unraveling the Light‐Activated Reaction Mechanism in a Catalytically Competent Key Intermediate of a Multifunctional Molecular Catalyst for Artificial Photosynthesis
title_full Unraveling the Light‐Activated Reaction Mechanism in a Catalytically Competent Key Intermediate of a Multifunctional Molecular Catalyst for Artificial Photosynthesis
title_fullStr Unraveling the Light‐Activated Reaction Mechanism in a Catalytically Competent Key Intermediate of a Multifunctional Molecular Catalyst for Artificial Photosynthesis
title_full_unstemmed Unraveling the Light‐Activated Reaction Mechanism in a Catalytically Competent Key Intermediate of a Multifunctional Molecular Catalyst for Artificial Photosynthesis
title_short Unraveling the Light‐Activated Reaction Mechanism in a Catalytically Competent Key Intermediate of a Multifunctional Molecular Catalyst for Artificial Photosynthesis
title_sort unraveling the light‐activated reaction mechanism in a catalytically competent key intermediate of a multifunctional molecular catalyst for artificial photosynthesis
topic Research Articles
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6772164/
https://www.ncbi.nlm.nih.gov/pubmed/31347251
http://dx.doi.org/10.1002/anie.201907247
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