Proton-Coupled Redox Switching in an Annulated π-Extended Core-Modified Octaphyrin

Tridib Sarma, Gakhyun Kim, Sajal Sen, Won Young Cha, Zhiming Duan, Matthew D. Moore, Vincent M. Lynch, Zhan Zhang, Dongho Kim, Jonathan L. Sessler

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

Proton-coupled electron transfer (PCET) is an important chemical and biological phenomenon. It is attractive as an on-off switching mechanism for redox-active synthetic systems but has not been extensively exploited for this purpose. Here we report a core-modified planar weakly antiaromatic/nonaromatic octaphyrin, namely, a [32]octaphyrin(1.0.1.0.1.0.1.0) (1) derived from rigid naphthobipyrrole and dithienothiophene (DTT) precursors, that undergoes proton-coupled two-electron reduction to produce its aromatic congener in the presence of HCl and other hydrogen halides. Evidence for the production of a [4n + 1] π-electron intermediate radical state is seen in the presence of trifluoroacetic acid. Electrochemical analyses provide support for the notion that protonation causes a dramatic anodic shift in the reduction potentials of octaphyrin 1, thereby facilitating electron transfer from halide anions (viz. I-, Br-, and, Cl-). Electron-rich molecules, such as tetrathiafulvene (TTF), phenothiazine (PTZ), and catechol, were also found to induce PCET in the case of 1. Both the oxidized and two-electron reduced forms of 1 were characterized by X-ray diffraction analyses in the solid state and in solution via spectroscopic means.

Original languageEnglish
Pages (from-to)12111-12119
Number of pages9
JournalJournal of the American Chemical Society
Volume140
Issue number38
DOIs
Publication statusPublished - 2018 Sep 26

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Oxidation-Reduction
Protons
Electrons
Chemical Phenomena
Trifluoroacetic acid
Biological Phenomena
Trifluoroacetic Acid
Protonation
X-Ray Diffraction
Anions
Hydrogen
Negative ions
X ray diffraction
Molecules

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Sarma, T., Kim, G., Sen, S., Cha, W. Y., Duan, Z., Moore, M. D., ... Sessler, J. L. (2018). Proton-Coupled Redox Switching in an Annulated π-Extended Core-Modified Octaphyrin. Journal of the American Chemical Society, 140(38), 12111-12119. https://doi.org/10.1021/jacs.8b06938
Sarma, Tridib ; Kim, Gakhyun ; Sen, Sajal ; Cha, Won Young ; Duan, Zhiming ; Moore, Matthew D. ; Lynch, Vincent M. ; Zhang, Zhan ; Kim, Dongho ; Sessler, Jonathan L. / Proton-Coupled Redox Switching in an Annulated π-Extended Core-Modified Octaphyrin. In: Journal of the American Chemical Society. 2018 ; Vol. 140, No. 38. pp. 12111-12119.
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Sarma, T, Kim, G, Sen, S, Cha, WY, Duan, Z, Moore, MD, Lynch, VM, Zhang, Z, Kim, D & Sessler, JL 2018, 'Proton-Coupled Redox Switching in an Annulated π-Extended Core-Modified Octaphyrin', Journal of the American Chemical Society, vol. 140, no. 38, pp. 12111-12119. https://doi.org/10.1021/jacs.8b06938

Proton-Coupled Redox Switching in an Annulated π-Extended Core-Modified Octaphyrin. / Sarma, Tridib; Kim, Gakhyun; Sen, Sajal; Cha, Won Young; Duan, Zhiming; Moore, Matthew D.; Lynch, Vincent M.; Zhang, Zhan; Kim, Dongho; Sessler, Jonathan L.

In: Journal of the American Chemical Society, Vol. 140, No. 38, 26.09.2018, p. 12111-12119.

Research output: Contribution to journalArticle

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AU - Sarma, Tridib

AU - Kim, Gakhyun

AU - Sen, Sajal

AU - Cha, Won Young

AU - Duan, Zhiming

AU - Moore, Matthew D.

AU - Lynch, Vincent M.

AU - Zhang, Zhan

AU - Kim, Dongho

AU - Sessler, Jonathan L.

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