Synthesis and characterization of an immobilizable photochemical molecular device for H-2-generation

With [Ru-II(bpyMeP)(2)tpphzPtCl(2)](2+) (4) a molecular photocatalyst has been synthesized for visible-light-driven H-2-evolution. It contains the ligand bpyMeP (4,4'-bis(diethyl-(methylene)-phosphonate)-2,2'-bipyridine) with phosphate ester groups as precursors for the highly potent phosphonate anchoring groups, which can be utilized for immobilization of the catalyst on metal-oxide semiconductor surfaces. The synthesis was optimized with regard to high yields, bpyMeP was fully characterized and a solid-state structure could be obtained. Photophysical studies showed that the photophysical properties and the localization of the excited states are not altered compared to similar Ru-complexes without anchoring group precursors. (4) was even more active in homogenous catalysis experiments than [RuII(tbbpy)(2)tpphzPtCl(2)](2+) (6) with tbbpy (4,4'-bis(tbutyl)-2,2'-bipyridine) as peripheral ligands. After hydrolysis (4) was successfully immobilized on NiO, suggesting that an application in photoelectrosynthesis cells is feasible.