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journal article·2024-10Open access

Ultrafast Two‐Color X‐Ray Emission Spectroscopy Reveals Excited State Landscape in a Base Metal Dyad

Michal Nowakowski, Marina Huber‐Gedert, Hossam Elgabarty, Aleksandr Kalinko, Jacek Kubicki, Ahmet Kertmen, Natalia Lindner, Dmitry Khakhulin, Frederico A. Lima, Tae‐Kyu Choi, Mykola Biednov, Lennart Schmitz, Natalia Piergies, Peter Zalden, Katharina Kubicek, Angel Rodriguez‐Fernandez, Mohammad Alaraby Salem, Sophie E. Canton, Christian Bressler, Thomas D. Kühne, Wojciech Gawelda, Matthias Bauer

Advanced Science· Volume 11· Issue 38
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Source abstract

Abstract

Abstract Effective photoinduced charge transfer makes molecular bimetallic assemblies attractive for applications as active light‐induced proton reduction systems. Developing competitive base metal dyads is mandatory for a more sustainable future. However, the electron transfer mechanisms from the photosensitizer to the proton reduction catalyst in base metal dyads remain so far unexplored. A Fe─Co dyad that exhibits photocatalytic H2 production activity is studied using femtosecond X‐ray emission spectroscopy, complemented by ultrafast optical spectroscopy and theoretical time‐dependent DFT calculations, to understand the electronic and structural dynamics after photoexcitation and during the subsequent charge transfer process from the FeII photosensitizer to the cobaloxime catalyst. This novel approach enables the simultaneous measurement of the transient X‐ray emission at the iron and cobalt K‐edges in a two‐color experiment. With this methodology, the excited state dynamics are correlated to the electron transfer processes, and evidence of the Fe→Co electron transfer as an initial step of proton reduction activity is unraveled.
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Research context

Catalysis & surfaces

OpenAlex topics: X-ray Spectroscopy and Fluorescence Analysis · Electron and X-Ray Spectroscopy Techniques · Photochemistry and Electron Transfer Studies

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Chemistry Department and Center for Sustainable Systems Design (CSSD) Faculty of Science Paderborn University Warburger Straße 100 33098 Paderborn Germany

Deutsches Elektronen‐Synchrotron DESY 22607 Notkestr. 85 Hamburg Germany

Faculty of Physics Adam Mickiewicz University, Poznań Uniwersytetu Poznańskiego 2 Poznań 61‐614 Poland

European X‐Ray Free‐Electron Laser Facility GmbH 22869 Holzkoppel 4 Schenefeld Germany

PAL‐XFEL Jigok‐ro 127–80 Pohang 37673 Republic of Korea

Institute of Nuclear Physics Polish Academy of Sciences Kraków 31‐342 Poland

The Hamburg Centre for Ultrafast Imaging 22761 Luruper Chaussee 149 Hamburg Germany

Fachbereich Physik Universität Hamburg 22607 Notkestraße 9–11 Hamburg Germany

Department of Chemistry Technical University of Denmark Kongens Lyngby DK‐2800 Denmark

Center for Advanced Systems Understanding (CASUS) Helmholtz‐Zentrum Dresden‐Rossendorf 02826 Untermarkt 20 Görlitz Germany

Institute of Artificial Intelligence, Chair of Computational System Sciences Technische Universität Dresden 01187 Helmholtzstr. 10 Dresden Germany

IMDEA Nanociencia Calle Faraday 9 Madrid 28049 Spain

Departamento de Química Universidad Autónoma de Madrid Campus Cantoblanco Madrid 28047 Spain

Funding

Deutsche Forschungsgemeinschaft · Bundesministerium für Bildung und Forschung

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