Toward highlighting the ultrafast electron transfer dynamics at the optically dark sites of photocatalysts

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

Research output: Contribution to journalArticle

38 Citations (Scopus)

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
Pages (from-to)1972-1976
Number of pages5
JournalJournal of Physical Chemistry Letters
Volume4
Issue number11
DOIs
Publication statusPublished - Jun 26 2013

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Keywords

  • electron transfer
  • excited-state structure
  • hydrogen evolution
  • photocatalysis
  • transient X-ray absorption spectroscopy
  • ultrafast structural dynamics

ASJC Scopus subject areas

  • Materials Science(all)
  • Physical and Theoretical Chemistry

Cite this

Canton, S. E., Zhang, X., Zhang, J., Van Driel, T. B., Kjaer, K. S., Haldrup, K., Chabera, P., Harlang, T., Suarez-Alcantara, K., Liu, Y., Pérez, J., Bordage, A., Pápai, M., 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. Journal of Physical Chemistry Letters, 4(11), 1972-1976. https://doi.org/10.1021/jz401016h