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

Canton, Sophie LU ; Zhang, Xiaoyi; Zhang, Jianxin LU ; van Driel, Tim B.; Kjaer, Kasper S.; Haldrup, Kristoffer; Chabera, Pavel LU ; Harlang, Tobias LU ; Suarez Alcantara, Karina LU and Liu, Yizhu LU , et al. (2013) In The Journal of Physical Chemistry Letters 4(11). p.1972-1976
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 angstrom. The analysis is supported by simulations based on density functional theory... (More)
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 angstrom. 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. (Less)
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Contribution to journal
publication status
published
subject
in
The Journal of Physical Chemistry Letters
volume
4
issue
11
pages
1972 - 1976
publisher
The American Chemical Society
external identifiers
  • wos:000320214600036
  • pmid:26283136
  • scopus:84879222784
ISSN
1948-7185
DOI
10.1021/jz401016h
language
English
LU publication?
yes
id
1706e972-1179-49ea-83d7-9645961885d6 (old id 3983082)
date added to LUP
2013-09-11 16:19:54
date last changed
2019-04-02 02:20:28
@article{1706e972-1179-49ea-83d7-9645961885d6,
  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 angstrom. 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.},
  author       = {Canton, Sophie and Zhang, Xiaoyi and Zhang, Jianxin and van Driel, Tim B. and Kjaer, Kasper S. and Haldrup, Kristoffer and Chabera, Pavel and Harlang, Tobias and Suarez Alcantara, Karina and Liu, Yizhu and Perez Tuero, Jorge and Bordage, Amelie and Papai, Matyas and Vanko, Gyoergy and Jennings, Guy and Kurtz, Charles A. and Rovezzi, Mauro and Glatzel, Pieter and Smolentsev, Grigory and Uhlig, Jens and Dohn, Asmus O. and Christensen, Morten and Galler, Andreas and Gawelda, Wojciech and Bressler, Christian and Lemke, Henrik T. and Moller, Klaus B. and Nielsen, Martin M. and Lomoth, Reiner and Wärnmark, Kenneth and Sundström, Villy},
  issn         = {1948-7185},
  language     = {eng},
  number       = {11},
  pages        = {1972--1976},
  publisher    = {The American Chemical Society},
  series       = {The Journal of Physical Chemistry Letters},
  title        = {Toward Highlighting the Ultrafast Electron Transfer Dynamics at the Optically Dark Sites of Photocatalysts},
  url          = {http://dx.doi.org/10.1021/jz401016h},
  volume       = {4},
  year         = {2013},
}