Abstract
Herein, two complexes: Pyrene modified photosensitizer (RuPy) and catalyst (ReCOPy) were synthetized and combined to form a novel bimetallic supramolecular assembly RuPy•••ReCOPy via a combination of π-π stacking and hydrogen bond interactions. This supramolecular assembly was further characterized by electrochemical and spectroscopic techniques in order to determine its redox and photochemical properties. This novel RuPy•••ReCOPy supramolecular assembly was demonstrated to display a high level of performance for the photocatalytic conversion of CO2 conversion into CO with turn over frequency and CO quantum yield much higher (TOF: 18 h-1 , ΦCO: 0.77) than the value obtained for the benchmark system Ru(bpy)3Cl2 (Ru) with Re(bpy)(CO)3Cl (ReCO) (5.3 h-1 , ΦCO : 0.38). Time resolved spectroscopy and Density Functional Theory calculations revealed that an electron transfer mechanism is at the origin of the highly photocatalytic performance of RuPy•••ReCOPy.