jp9b07830_si_001.pdf (732.76 kB)
Light-Driven Redox Activation of CO2- and H2‑Activating Complexes in a Self-Assembled Triad
journal contribution
posted on 2019-12-13, 19:25 authored by Nathan
T. La Porte, Davis B. Moravec, Richard D. Schaller, Michael D. HopkinsWe report a self-assembled triad for artificial photosynthesis
composed 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–porphyrin
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
time scale 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 transient absorption spectroscopy
in the visible, near-infrared, and mid-infrared spectral regions.
The behavior of the triad was compared with 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.
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absorption spectroscopycarbon-dioxide reduction catalystcharge-transfer behaviorultrafast charge transferSelf-Assembled Triadredox equivalentsself-assembled triadchromophoretime scalecharge-separated lifetimewater-gas shift reactionCO 2charge-separated stateLight-Driven Redox Activationcarbon dioxide binding stepsrhenium diimine tricarbonyl acceptortriad results
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