Hannover 2016 – wissenschaftliches Programm
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MO: Fachverband Molekülphysik
MO 19: Posters 4: Novelties in Molecular Physics: Femtosecond Spectroscopy, Molecular Clusters, Cold Molecules and Helium Droplets
MO 19.5: Poster
Donnerstag, 3. März 2016, 16:30–19:00, Empore Lichthof
Excited state dynamics of dimetallic [Ag2(dcpm)2]2+ in gas- and solution phase — •Florian Bäppler1, Sebastian Kruppa2, Christoph Riehn2, and Rolf Diller1 — 1Dept. of Physics, — 2Dept. of Chemistry, Univ. Kaiserslautern, 67663 Germany
[Ag2(dcpm)2]2+ (dcpm = bis(dicyclohexylphosphanyl)) is a prototype example for luminescent binuclear Ag(I) complexes exhibiting interesting photophysical and photochemical properties. Due to the absence of ligand-centered UV-chromophors it serves as a good model system for the investigation of argentophilic metal-metal interactions [1]. Here, we investigate the excited state dynamics of [Ag2(dcpm)2]2+ in parallel in gas phase by fs transient photofragmentation [2], and in solution (CH3CN) by fs transient absorption [2] at room temperature. Surprisingly, both methods reveal similar deactivation kinetics, characterized by a triple exponential decay ( 1, 10 and 350 ps) after excitation of the silver-centered 1MC(dσ*-pσ) state at 260 nm. This suggests similar excited state deactivation processes in gas- and solution phase and consequently little influence of solvent (CH3CN) molecules. In particular, fast exciplex formation [[Ag2(dcpm)2]2+/CH3CN]* as suggested [3] for an analog Au2-complex can be excluded as essential component of the reaction coordinate, although it could occur concomitantly as a side effect in solution. Consequences for the interplay between photophysics and complex-solvent interaction are discussed.
[1] Schmidbaur et al., Angew. Chem. Int. Ed. 2015, 54, 746-784.
[2] Imanbaew et al., Chemical Physics 2014, 442, 53-61.
[3] Ma et al., Chemistry-A European Journal 2015, 21, 13888-13893.