Herein, a new supramolecular photocatalyst RuRe3 containing three Re(dmb)CO 3 Cl (dmb = 4,4'-dimethyl-2,2'-bipyridine) (Re) building blocks connected through an ethylene bridge to one [Ru(dmb) 3 ] 2 + -unit (Ru) is presented. We investigated the photophysical properties of this novel tetranuclear complex and compared these to compounds with one (RuRe) and two (RuRe2) catalytic units. Under irradiation, all three photocatalysts exhibit high activity and photostability for the reduction of CO 2 to CO, with RuRe3 achieving the highest turnover number (11800) reported to date for a Re(I)/Ru(II)containing homogeneous catalyst. This tetranuclear complex is especially superior at small catalyst concentrations, which is attributed to an efficient second electron transfer via an intramolecular mechanism. Intermolecular electron transfer from small and mobile Re to RuRe motifs are found to also increase the catalytic performance of the system to a similar level (turnover number = 12100). These synergistic effects are attributed to an improved catalytic cycle, stabilizing the bi-and tetrametallic complexes by providing the electrons quickly and effectively. Since the second electron provision is not finally clarified for molecular systems until today, our photocatalytic studies present important insights into this crucial step. Further, these investigations should be considered for the design and synthesis of new and efficient supramolecular CO 2 -reducing photocatalysts.
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