Erlangen 2022 – scientific programme
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MO: Fachverband Molekülphysik
MO 5: Femtosecond Spectroscopy I
MO 5.3: Talk
Tuesday, March 15, 2022, 11:15–11:30, MO-H6
Ultrafast Spectroelectrochemistry in the Visible Spectral Range on a Perylene Bisimide Cyclophane — •Rebecca Fröhlich1, Jessica Rühe2, Frank Würthner2, and Tobias Brixner1 — 1Institut für Physikalische und Theoretische Chemie, Universität Würzburg, Am Hubland, 97074 Würzburg — 2Institut für Organische Chemie, Universität Würzburg, Am Hubland, 97074 Würzburg
With spectroelectrochemistry the oxidation states of molecules can be investigated under potential control without the need of a chemical oxidant/reductant. In our setup we combine spectroelectrochemistry with ultrafast spectroscopy and use broadband excitation in the visible spectral range for TA and 2D spectroelectrochemistry [1]. Here we describe new experiments on a perylene bisimide cyclophane. For electrolysis we employ a custom-built flow cell with the organic solvent dichloromethane and the supporting electrolyte TBAHFP. The meta-xylene linked cyclophane under investigation creates a rigid system with a small distance of 5 Å between the aromatic units which leads to a coupling of the first excited electronic state with the first vibrational state [2]. Our time-resolved data show symmetry-breaking charge transfer leading to the generation of radical anionic and cationic species. Upon reduction of the cyclophane the dynamics change depending on the applied potential.
[1] J. Heitmüller et al., Spectrochim. Acta Part A, 253, 119567 (2021)
[2] J. Rühe et al., Organic Materials, 2, 149-158 (2020)