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

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

doi:10.1021/acs.jpcb.9b07830

Title: Light-Driven Redox Activation of CO₂- and H₂-Activating Complexes in a Self-Assembled Triad

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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. Here, 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.

Authors:

^[1]; Moravec, Davis B. ^[2];

^[3];

^[4]

Univ. of Chicago, IL (United States); Northwestern Univ., Evanston, IL (United States)
Univ. of Chicago, IL (United States); Donaldson Co., Bloomington, MN (United States)
Northwestern Univ., Evanston, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
Univ. of Chicago, IL (United States)

Publication Date:: Fri Nov 15 00:00:00 EST 2019

Research Org.:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1606540

Grant/Contract Number:: AC02-06CH11357; DGE-0638477; FG02-07-ER15910

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry

Additional Journal Information:: Journal Volume: 123; Journal Issue: 51; Journal ID: ISSN 1520-6106

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; redox reactions; absorption; catalysts; quenching; excited states

Citation Formats


                    La Porte, Nathan T., Moravec, Davis B., Schaller, Richard D., and Hopkins, Michael D. Light-Driven Redox Activation of CO2- and H2-Activating Complexes in a Self-Assembled Triad.  United States: N. p., 2019. 
Web.  doi:10.1021/acs.jpcb.9b07830.

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                    La Porte, Nathan T., Moravec, Davis B., Schaller, Richard D., & Hopkins, Michael D. Light-Driven Redox Activation of CO2- and H2-Activating Complexes in a Self-Assembled Triad.  United States.  https://doi.org/10.1021/acs.jpcb.9b07830

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                    La Porte, Nathan T., Moravec, Davis B., Schaller, Richard D., and Hopkins, Michael D. Fri .  
"Light-Driven Redox Activation of CO2- and H2-Activating Complexes in a Self-Assembled Triad".  United States.  https://doi.org/10.1021/acs.jpcb.9b07830.  https://www.osti.gov/servlets/purl/1606540.

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@article{osti_1606540,

  title        = {Light-Driven Redox Activation of CO2- and H2-Activating Complexes in a Self-Assembled Triad},

  author       = {La Porte, Nathan T. and Moravec, Davis B. and Schaller, Richard D. and Hopkins, Michael D.},

  abstractNote = {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. Here, 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.},

  doi          = {10.1021/acs.jpcb.9b07830},

  journal      = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},

  number       = 51,

  volume       = 123,

  place        = {United States},

  year         = {Fri Nov 15 00:00:00 EST 2019},

  month        = {Fri Nov 15 00:00:00 EST 2019}

}

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Title: Light-Driven Redox Activation of CO2- and H2-Activating Complexes in a Self-Assembled Triad

Abstract

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Title: Light-Driven Redox Activation of CO₂- and H₂-Activating Complexes in a Self-Assembled Triad