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

Research output: Contribution to journalArticlepeer-review

26 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
Externally publishedYes

Keywords

  • oriented internal electrostatic fields
  • electrostatic fields
  • thermodynamics
  • chemical reactions
  • ground-state chemistry
  • excited-state reactivity
  • photochemical
  • CO2
  • CO2 capture

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