Erlangen 2022 – wissenschaftliches Programm
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MO: Fachverband Molekülphysik
MO 15: Poster 2
MO 15.6: Poster
Mittwoch, 16. März 2022, 16:30–18:30, P
Ultrafast dynamics of [Ru(bipyridine)2(nicotinamide)2]2+ and photoinduced formation of its water splitting adducts in gas and liquid phase — •Roumany Israil1, Lars Schüssler2, Patrick Hütchen1, Werner Thiel1, Rolf Diller2, and Christoph Riehn1 — 1TU Kaiserslautern, FB Chemie, 52, 54 — 2TU Kaiserslautern, FB Physik, 46
A fundamental understanding of the kinetics of RuII polypyridyl complexes is essential to exploit their photochemical applicability in areas such as medicine (photoactivatable prodrugs) and material science (photovoltaics/catalysis). In particular, the monodentate ligand nicotinamide in [Ru(bpy)2(na)2]2+ (bpy = bipyridine) enables the efficient population of the dissociative triplet metal-centered (3MC) state on a sub-ps time scale, allowing for fast photosolvolysis and subsequent reactions of the complex. Here, the photoactive [Ru(bpy)2(na)2]2+ , including its related photoproducts such as the penta-coordinate intermediate (PCI, [Ru(bpy)2(na)]2+) and the monoaqua species [Ru(bpy)2(na)(H2O)]2+ were object to transient ion action spectroscopy in gas phase and transient absorption spectroscopy in solution. In gas phase, dynamics (τ1 ∼0.6 ps, τ2 ∼3 ps) of [Ru(bpy)2(na)2]2+ is in line with the liquid phase. However, prominent larger time components (∼10 ps, 100-400 ps) found in solution, do not appear in gas phase, allowing their unequivocal assignment to intermolecular processes. This study is an important step towards controlling the efficiency and photoactivity of RuII polypyridyl complexes by tailored ligands design.