Heidelberg 2015 – wissenschaftliches Programm

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MO: Fachverband Molekülphysik

MO 11: Posters 2: Novelties in Molecular Physics

MO 11.4: Poster

Dienstag, 24. März 2015, 17:00–19:00, C/Foyer

Ultrafast photodynamics of a trinuclear palladium complex studied by femtosecond time-resolved transient UV/Vis and mid-IR spectroscopy — •Fabian Rupp¹, Zimmer Manuel¹, Yvonne Schmitt¹, Katharina Chevalier¹, Dimitri Imanbaew¹, Yevgeniy Nosenko¹, Christoph Riehn¹, Frank Breher², Markus Gerhards¹, Wim Klopper², and Rolf Diller¹ — ¹TU Kaiserslautern, 67663 Kaiserslautern — ²Karlsruhe Institute of Technology, 76131 Karlsruhe

Multinuclear transition metal complexes with their promising cooperative effects are very attractive for new electronic devices or chemical catalysis. Here we investigated the photophysical properties of a trinuclear Pd₃ complex [Pd₃{Si(mt^Me)₃}₂] [1] solved in DMSO-d₆. After electronic excitation at 330 nm the system undergoes a photocycle with ultrafast formation of a long lived luminescent triplet state ³A₁ (τ_fluo = 1.4 – 1.7 µs, λ_fluo =  675 nm).[2] The ultrafast formation of the emissive electronic state is monitored by fs UV/Vis spectroscopy (380 fs) in solution and photofragmentation (200 fs) for the ionic complex in gas phase, whereas vibrational cooling (τ_VC = 7.8 ps) is clearly observed via fs mid-IR spectroscopy in solution. Additional step-scan FTIR measurements exhibit no further structural changes on longer time scales (ns to µs). The experimental vibrational spectra are in very good agreement with TD-DFT calculations.
[1] F. Armbruster et al., Chem. Commun., 2011, 47, 221
[2] Y. Schmitt et al., PCCP, 2014, 16, 8332