Ultrafast intramolecular relaxation and wave-packet motion in a ruthenium-based supramolecular photocatalyst.

The hydrogen-evolving photocatalyst (tbbpy)2 Ru(tpphz)Pd(Cl)2 (tbbpy=4,4'-di-tert-butyl-2,2'-bipyridine, tpphz=tetrapyrido[3,2-a:2',3'-c:3'',2''-h:2''',3'''-j]phenazine) shows excitation-wavelength-dependent catalytic activity, which has been correlated to the localization of the initial excitation within the coordination sphere. In this contribution the excitation-wavelength dependence of the early excited-state relaxation and the occurrence of vibrational coherences are investigated by sub-20 fs transient absorption spectroscopy and DFT/TDDFT calculations. The comparison with the mononuclear precursor (tbbpy)2 Ru(tpphz) highlights the influence of the catalytic center on these ultrafast processes. Only in the presence of the second metal center, does the excitation of a (1) MLCT state localized on the central part of the tpphz bridge lead to coherent wave-packet motion in the excited state.