Oriented Internal Electrostatic Fields Cooperatively Promote Ground- And Excited-State Reactivity: A Case Study in Photochemical CO2 Capture

Mitchell T. Blyth, Benjamin B. Noble, Isabella C. Russell, Michelle L. Coote*

*Corresponding author for this work

    Research output: Contribution to journalArticlepeer-review

    52 Citations (Scopus)

    Abstract

    Oriented electrostatic fields can exert catalytic effects upon both the kinetics and the thermodynamics of chemical reactions; however, the vast majority of studies thus far have focused upon ground-state chemistry and rarely consider any more than a single class of reaction. In the present study, we first use density functional theory (DFT) calculations to clarify the mechanism of CO2 storage via photochemical carboxylation of o-alkylphenyl ketones, originally proposed by Murakami et al. (J. Am. Chem. Soc. 2015, 137, 14063); we then demonstrate that oriented internal electrostatic fields arising from remote charged functional groups (CFGs) can selectively and cooperatively promote both ground- and excited-state chemical reactivity at all points along the revised mechanism, in a manner otherwise difficult to access via classical substituent effects. What is particularly striking is that electrostatic field effects upon key photochemical transitions are predictably enhanced in increasingly polar solvents, thus overcoming a central limitation of the electrostatic catalysis paradigm. We explain these observations, which should be readily extendable to the ground state.

    Original languageEnglish
    Pages (from-to)606-613
    Number of pages8
    JournalJournal of the American Chemical Society
    Volume142
    Issue number1
    DOIs
    Publication statusPublished - 8 Jan 2020

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