摘要： We report a self-assembled triad for artificial photosynthesis comprised of a chromophore, carbon-dioxide reduction catalyst, and hydrogen-oxidation complex, which is designed to operate without conventional sacrificial redox equivalents. Excitation of the zinc–tetraphenylporphyrin chromophore of the triad results in ultrafast charge transfer between a tungsten–alkylidyne donor and a rhenium diimine tricarbonyl acceptor, producing a charge-separated state that persists on the timescale of tens of nanoseconds and is thermodynamically capable of the primary dihydrogen and carbon dioxide binding steps for initiating the reverse water-gas shift reaction. The charge-transfer behavior of this system was probed using time-resolved fluorescence and transient absorption spectroscopy in the visible, near-infrared, and mid-infrared spectral regions. The behavior of the triad was compared to that of the zinc porphyrin–rhenium diimide dyad; the triad was found to have a significantly longer charge-separated lifetime than other previously reported porphyrin–rhenium diimine compounds.