TY - JOUR
T1 - Light-Driven Redox Activation of CO2- A nd H2-Activating Complexes in a Self-Assembled Triad
AU - La Porte, Nathan T.
AU - Moravec, Davis B.
AU - Schaller, Richard D.
AU - Hopkins, Michael D.
PY - 2019/12/26
Y1 - 2019/12/26
N2 - We 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.
AB - We 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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U2 - 10.1021/acs.jpcb.9b07830
DO - 10.1021/acs.jpcb.9b07830
M3 - Article
C2 - 31729229
AN - SCOPUS:85076886601
VL - 123
SP - 10980
EP - 10989
JO - Journal of Physical Chemistry B
JF - Journal of Physical Chemistry B
SN - 1520-6106
IS - 51
ER -