X-ray Absorption Spectroscopy of Ground and Excited Rhenium?Carbonyl?Diimine Complexes: Evidence for a Two-Center Electron Transfer

Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F13%3A00388677" target="_blank" >RIV/61388955:_____/13:00388677 - isvavai.cz</a>
Result on the web
<a href="http://dx.doi.org/10.1021/jp3106502" target="_blank" >http://dx.doi.org/10.1021/jp3106502</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/jp3106502" target="_blank" >10.1021/jp3106502</a>

Result language
angličtina
Original language name
X-ray Absorption Spectroscopy of Ground and Excited Rhenium?Carbonyl?Diimine Complexes: Evidence for a Two-Center Electron Transfer
Original language description
Steady-state and picosecond time-resolved X-ray absorption spectroscopy is used to study the ground and lowest triplet states of [ReX(CO)3(bpy)]n+, X = Etpy (n = 1), Cl, or Br (n = 0). We demonstrate that the transient spectra at both the Re L3- and Br K-edges show the emergence of a pre-edge feature, absent in the ground-state spectrum, which is associated with the electron hole created in the highest occupied molecular orbital following photoexcitation. Importantly, these features have the same dynamics, confirming previous predictions that the low-lying excited states of these complexes involve a two-center charge transfer from both the Re and the ligand, X. We also demonstrate that the DFT optimized ground and excited structures allow us to reproduce the experimental XANES and EXAFS spectra. The ground-state structural refinement shows that the Br atom contributes very little to the latter, whereas the Re-C-O scattering paths are dominant due to the so-called focusing effect. For t
Czech name
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Czech description
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Type
J<sub>x</sub> - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)
CEP classification
CF - Physical chemistry and theoretical chemistry
OECD FORD branch
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Project
<a href="/en/project/LD11086" target="_blank" >LD11086: Quantum chemical interpretation and prediction of spectral characteristics of heavy transition metal complexes</a><br>
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year
2013
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

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