Journal article
Toward Highlighting the Ultrafast Electron Transfer Dynamics at the Optically Dark Sites of Photocatalysts
Lund University1
SLAC National Accelerator Laboratory2
Uppsala University3
Argonne National Laboratory4
Department of Physics, Technical University of Denmark5
University of Copenhagen6
Hungarian Academy of Sciences7
European Synchrotron Radiation Facility8
Department of Chemistry, Technical University of Denmark9
Physical and Biophysical Chemistry, Department of Chemistry, Technical University of Denmark10
European XFEL11
...and 1 moreBuilding a detailed understanding of the structure–function relationship is a crucial step in the optimization of molecular photocatalysts employed in water splitting schemes. The optically dark nature of their active sites usually prevents a complete mapping of the photoinduced dynamics. In this work, transient X-ray absorption spectroscopy highlights the electronic and geometric changes that affect such a center in a bimetallic model complex.
Upon selective excitation of the ruthenium chromophore, the cobalt moiety is reduced through intramolecular electron transfer and undergoes a spin flip accompanied by an average bond elongation of 0.20 ± 0.03 Å. The analysis is supported by simulations based on density functional theory structures (B3LYP*/TZVP) and FEFF 9.0 multiple scattering calculations.
More generally, these results exemplify the large potential of the technique for tracking elusive intermediates that impart unique functionalities in photochemical devices.
Language: | English |
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Publisher: | American Chemical Society (ACS) |
Year: | 2013 |
Pages: | 1972-1976 |
ISSN: | 19487185 |
Types: | Journal article |
DOI: | 10.1021/jz401016h |
ORCIDs: | Haldrup, Martin Kristoffer , Dohn, Asmus Ougaard , Møller, Klaus Braagaard and Nielsen, Martin Meedom |