Generation of a stable supramolecular hydrogen evolving photocatalyst by alteration of the catalytic center

A new dyad consisting of a Ru II chromophore, a tetrapyridophenazine bridging ligand and a Rh(Cp*)Cl catalytic center, [Ru(tbbpy) 2 (tpphz)Rh(Cp*)Cl]Cl(PF 6 ) 2 , acts as durable photocatalyst for hydrogen production from water. Catalytic activity is observed for more than 650 hours. Electrochemical investigations reveal that up to two electrons can be transferred to the catalytic center by a thermodynamically favorable intramolecular process, which has so far not been reported for similar tpphz based supramolecular photocatalysts. Additionally, mercury poisoning tests indicate that the new dyad works as a homogeneous photocatalyst. The change of the catalytic center from MX 2 to RhCp*Cl leads to a stability boost in [(tbbpy) 2 Ru(tpphz)] based supramolecular photocatalysts.