SAMOP 2021 – scientific programme
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MO: Fachverband Molekülphysik
MO 7: Poster 1
MO 7.10: Poster
Thursday, September 23, 2021, 17:30–19:30, P
Intrinsic Electronic Dynamics of of RuII-Polypyridyl Complexes Studied by Ion Spectroscopy — •Roumany Israil1, Lars Schüssler3, Patrick Hütchen2, Werner Thiel2, Rolf Diller3, and Christoph Riehn1 — 1FB Chemie, TU Kaiserslautern, Erwin-Schrödingerstr. 52 — 2FB Chemie, 54 — 3FB Physik, 46
RuII-polypyridyl complexes are featured in a wide range of applications in the areas of medicine (photoactivatable prodrugs) and material science (photovoltaics/catalysis). Tailored ligand design enables the control of their efficiency and photoactivity by tuning the relative energies of the 3MLCT and 3MC states. A selected series of RuII-polypyridyl complexes in the type of [Ru(y-bpy)2(x-py)2]2+ (bpy = (2,2-bi)pyridine), where x/y are varying substituents of different electronic donating/withdrawing character, were examined by a combination of mass spectrometry and laser spectroscopy in the frequency and time domain in an ion trap. Here, static absorption spectra were recorded by determining fragment ion yields as a function of laser wavelength (UV photodissociation spectra) and compared to TD-DFT calculations to characterize the electronic transitions. The femtosecond dynamics were elucidated via a pump-probe scheme recording excited-state lifetimes. Electron withdrawing substituents on the pyridine chromophore were found to destabilize the RuII-pyridine bond in the ground-state while stabilizing electronically excited-state 3MC. Electron-donating substituents on bpy are observed to stabilize the coordinative bond, while stabilizing the 3MLCT-state resulting in longer excited-state lifetimes.