Insights into the different mechanistic stages of light-induced hydrogen evolution of a 5,5'-bisphenanthroline linked RuPt complex.

Herein, the synthesis in conjunction with the structural, electrochemical, and photophysical characterization of a 5,5'-bisphenanthroline (phenphen) linked heterodinuclear RuPt complex (Ru(phenphen)Pt) and its light-driven hydrogen formation activity are reported. A single crystal X-ray diffraction (SC-XRD) analysis identified a perpendicular orientation of the two directly linked 1,10-phenanthroline moieties. The disruption of π-conjugation blocks intramolecular electron transfer as evidenced by a comparative time-resolved optical spectroscopy study of Ru(phenphen)Pt and the reference complexes Ru(phenphen) and Ru(phenphen)Ru. However, reductive quenching is observed in the presence of an external electron donor such as triethylamine. Irradiating Ru(phenphen)Pt with visible light (470 nm) leads to H2 formation. We discuss a potential mechanism that mainly proceeds via Pt colloids and provide indications that initial hydrogen generation may also proceed via a molecular pathway. As previous reports on related heterodinuclear RuPt-based photocatalysts revealed purely molecular hydrogen evolution, the present work thus highlights the role of the bridging ligand in stabilizing the catalytic center and consequently determining the mechanism of light-induced hydrogen evolution in these systems.

Carbene based photochemical molecular assemblies for solar driven hydrogen generation.

Novel photocatalysts based on ruthenium complexes with NHC (N-heterocyclic carbene)-type bridging ligands have been prepared and structurally and photophysically characterised. The identity of the NHC-unit of the bridging ligand was established unambiguously by means of X-ray structural analysis of a heterodinuclear ruthenium-silver complex. The photophysical data indicate ultrafast intersystem crossing into an emissive and a non-emissive triplet excited state after excitation of the ruthenium centre. Exceptionally high luminescence quantum yields of up to 39% and long lifetimes of up to 2 µs are some of the triplet excited state characteristics. Preliminary studies into the visible light driven photocatalytic hydrogen formation show no induction phase and constant turnover frequencies that are independent on the concentration of the photocatalyst. In conclusion this supports the notion of a stable assembly under photocatalytic conditions.

Modified bibenzimidazole ligands as spectator ligands in photoactive molecular functional Ru-polypyridine units? Implications from spectroscopy.

The photophysical properties of Ruthenium-bipyridine complexes bearing a bibenzimidazole ligand were investigated. The nitrogens on the bibenzimidazole-ligand were protected, by adding either a phenylene group or a 1,2-ethandiyl group, to remove the photophysical dependence of the complex on the protonation state of the bibenzimidazole ligand. This protection results in the bibenzimidazole ligand contributing to the MLCT transition, which is experimentally evidenced by (resonance) Raman scattering in concert with DFT calculations for a detailed mode assignment in the (resonance) Raman spectra.