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A Photoactive Semisynthetic Metalloenzyme Exhibits Complete Selectivity for CO2 Reduction in Water

Abstract

A series of artificial metalloenzymes containing a ruthenium chromophore and [NiII(cyclam)]2+, both incorporated site-selectively, have been constructed within an azurin protein scaffold. These light-driven, semisynthetic enzymes do not evolve hydrogen, thus displaying complete selectivity for CO2 reduction to CO. Electrostatic effects rather than direct excited-state electron transfer dominate the ruthenium photophysics, suggesting that intramolecular electron transfer from photogenerated RuI to [NiII(cyclam)]2+ represents the first step in catalysis. Stern-Volmer analyses rationalize the observation that ascorbate is the only sacrificial electron donor that supports turnover. Collectively, these results highlight the important interplay of elements that must be considered when developing and characterizing molecular catalysts.

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Publication details

The article was received on 13 Feb 2018, accepted on 10 Apr 2018 and first published on 10 Apr 2018


Article type: Communication
DOI: 10.1039/C8CC01297K
Citation: Chem. Commun., 2018, Accepted Manuscript
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    A Photoactive Semisynthetic Metalloenzyme Exhibits Complete Selectivity for CO2 Reduction in Water

    C. R. Schneider, A. C. Manesis, M. J. Stevenson and H. S. Shafaat, Chem. Commun., 2018, Accepted Manuscript , DOI: 10.1039/C8CC01297K

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