Scientific article
English

Activationless Multiple-Site Concerted Proton–Electron Tunneling

Published inJournal of the American Chemical Society, vol. 140, no. 24, p. 7449-7452
Publication date2018-06-20
First online date2018-05-30
Abstract

The transfer of protons and electrons is key to energy conversion and storage, from photosynthesis to fuel cells. Increased understanding and control of these processes are needed. A new anthracene-phenol-pyridine molecular triad was designed to undergo fast photoinduced multiple-site concerted proton-electron transfer (MS-CPET), with the phenol moiety transferring an electron to the photoexcited anthracene and a proton to the pyridine. Fluorescence quenching and transient absorption experiments in solutions and glasses show rapid MS-CPET (3.2 × 1010 s-1 at 298 K). From 5.5 to 90 K, the reaction rate and kinetic isotope effect (KIE) are independent of temperature, with zero Arrhenius activation energy. From 145 to 350 K, there are only slight changes with temperature. This MS-CPET reaction thus occurs by tunneling of both the proton and electron, in different directions. Since the reaction proceeds without significant thermal activation energy, the rate constant indicates the magnitude of the electron/proton double tunneling probability.

Affiliation entities Not a UNIGE publication
Funding
  • National Institute of General Medical Sciences [5F32GM109637]
  • NIGMS NIH HHS [R01 GM050422]
Citation (ISO format)
BOWRING, Miriam A et al. Activationless Multiple-Site Concerted Proton–Electron Tunneling. In: Journal of the American Chemical Society, 2018, vol. 140, n° 24, p. 7449–7452. doi: 10.1021/jacs.8b04455
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Article (Published version)
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Additional URL for this publicationhttps://pubs.acs.org/doi/10.1021/jacs.8b04455
Journal ISSN0002-7863
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