Journal
FARADAY DISCUSSIONS
Volume 171, Issue -, Pages 259-273Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c4fd00035h
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Funding
- Swiss National Science Foundation [200021-135226]
- European Commission [290605]
- French National Research Agency (ANR, Labex program ARCANE) [ANR-11-LABX-0003-01]
- European Research Council (ERC) [306398]
- Russian Foundation for Basic Research [14-02-31555]
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In order to probe the structure of reaction intermediates of photochemical reactions a new setup for laser-initiated time-resolved X-ray absorption (XAS) measurements has been developed. With this approach the arrival time of each photon in respect to the laser pulse is measured and therefore full kinetic information is obtained. All X-rays that reach the detector are used to measure this kinetic information and therefore the detection efficiency of this method is high. The newly developed setup is optimized for timeresolved experiments in the microsecond range for samples with relatively low metal concentration (similar to 1mM). This setup has been applied to study a multicomponent photocatalytic system with a Co(dmgBF(2))(2) catalyst (dmg2(-) = dimethylglyoximato dianion), [Ru(bpy)(3)](2+) chromophore (bpy = 2,2'-bipyridine) and methyl viologen as the electron relay. On the basis of the analysis of hundreds of Co K-edge XAS spectra corresponding to different delay times after the laser excitation of the chromophore, the presence of a Co(I) intermediate is confirmed. The calculated X-ray transient signal for a model of Co(I) state with a 0.14 angstrom displacement of Co out of the dmg ligand plane and with the closest solvent molecule at a distance of 2.06 angstrom gives reasonable agreement with the experimental data.
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