Photocatalytic Reduction of Nicotinamide Co‐factor by Perylene Sensitized Rh III Complexes **

The ambitious goal of artificial photosynthesis is to develop active systems that mimic nature and use light to split water into hydrogen and oxygen. Intramolecular design concepts are particularly promising. Herein, we firstly present an intramolecular photocatalyst integrating a perylene‐based light‐harvesting moiety and a catalytic rhodium center ( Rh III phenPer ). The excited‐state dynamics were investigated by means of steady‐state and time‐resolved absorption and emission spectroscopy. The studies reveal that photoexcitation of Rh III phenPer yields the formation of a charge‐separated intermediate, namely Rh II phenPer ⋅ + , that results in a catalytically active species in the presence of protons.