Toward Highlighting the Ultrafast Electron Transfer Dynamics at the Optically Dark Sites of Photocatalysts

Sophie E. Canton, Xiaoyi Zhang, Jianxin Zhang, Tim Brandt van Driel, Kasper S. Kjaer, Martin Kristoffer Haldrup, Pavel Chabera, Tobias Harlang, Karina Suarez-Alcantara, Yizhu Liu, Jorge Pérez, Amélie Bordage, Mátyás Imre Pápai, György Vankó, Guy Jennings, Charles A. Kurtz, Mauro Rovezzi, Pieter Glatzel, Grigory Smolentsev, Jens UhligAsmus Ougaard Dohn, Morten Christensen, Andreas Galler, Wojciech Gawelda, Christian Bressler, Henrik T. Lemke, Klaus Braagaard Møller, Martin Meedom Nielsen, Reiner Lomoth, Kenneth Wärnmark, Villy Sundström

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Abstract

Building 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.
Original languageEnglish
JournalThe Journal of Physical Chemistry Letters
Volume4
Issue number11
Pages (from-to)1972-1976
ISSN1948-7185
DOIs
Publication statusPublished - 2013

Keywords

  • Electron transfer
  • Photocatalysis
  • Hydrogen evolution
  • Transient X-ray absorption spectroscopy
  • Excited-state structure
  • Ultrafast structural dynamics

Cite this

Canton, S. E., Zhang, X., Zhang, J., Brandt van Driel, T., Kjaer, K. S., Haldrup, M. K., Chabera, P., Harlang, T., Suarez-Alcantara, K., Liu, Y., Pérez, J., Bordage, A., Pápai, M. I., Vankó, G., Jennings, G., Kurtz, C. A., Rovezzi, M., Glatzel, P., Smolentsev, G., ... Sundström, V. (2013). Toward Highlighting the Ultrafast Electron Transfer Dynamics at the Optically Dark Sites of Photocatalysts. The Journal of Physical Chemistry Letters, 4(11), 1972-1976. https://doi.org/10.1021/jz401016h