Light-Driven Redox Activation of CO2- A nd H2-Activating Complexes in a Self-Assembled Triad

Nathan T. La Porte, Davis B. Moravec, Richard D. Schaller, Michael D. Hopkins

Research output: Contribution to journalArticle

Abstract

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.

Original languageEnglish
Pages (from-to)10980-10989
Number of pages10
JournalJournal of Physical Chemistry B
Volume123
Issue number51
DOIs
Publication statusPublished - Dec 26 2019

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

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