Protonation-coupled redox reactions in planar antiaromatic meso-pentafluorophenyl-substituted o-phenylene-bridged annulated rosarins

Masatoshi Ishida, Soo Jin Kim, Christian Preihs, Kei Ohkubo, Jong Min Lim, Byung Sun Lee, Jung Su Park, Vincent M. Lynch, Vladimir V. Roznyatovskiy, Tridib Sarma, Pradeepta K. Panda, Chang Hee Lee, Shunichi Fukuzumi, Dongho Kim, Jonathan L. Sessler

Research output: Contribution to journalArticle

61 Citations (Scopus)

Abstract

Proton-coupled electron transfer (PCET) processes are among the most important phenomena that control a variety of chemical and biological transformations. Although extensively studied in a variety of natural systems and discrete metal complexes, PCET mechanisms are less well codified in the case of purely organic compounds. Here we report that a planar β,β′- phenylene-bridged hexaphyrin (1.0.1.0.1.0), a 24 π-electron antiaromatic species termed rosarin, displays unique redox reactivity on protonation. Specifically, treatment with acid (for example, HI) yields a 26 π-electron aromatic triprotonated monocationic species that is produced spontaneously via an intermediate - but stable - 25 π-electron non-aromatic triprotonated monoradical dication. This latter species is also produced on treatment of the original 24 π-electron antiaromatic starting material with HCl or HBr. The stepwise nature of the proton-coupled reduction observed in the planar rosarin stands in marked contrast to that seen for non-annulated rosarins and other ostensibly antiaromatic expanded porphyrinoids.

Original languageEnglish
Pages (from-to)15-20
Number of pages6
JournalNature chemistry
Volume5
Issue number1
DOIs
Publication statusPublished - 2013 Jan 1

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Redox reactions
Protonation
Electrons
Protons
Coordination Complexes
Metal complexes
Organic compounds
rosarin
Acids

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)

Cite this

Ishida, Masatoshi ; Kim, Soo Jin ; Preihs, Christian ; Ohkubo, Kei ; Lim, Jong Min ; Lee, Byung Sun ; Park, Jung Su ; Lynch, Vincent M. ; Roznyatovskiy, Vladimir V. ; Sarma, Tridib ; Panda, Pradeepta K. ; Lee, Chang Hee ; Fukuzumi, Shunichi ; Kim, Dongho ; Sessler, Jonathan L. / Protonation-coupled redox reactions in planar antiaromatic meso-pentafluorophenyl-substituted o-phenylene-bridged annulated rosarins. In: Nature chemistry. 2013 ; Vol. 5, No. 1. pp. 15-20.
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abstract = "Proton-coupled electron transfer (PCET) processes are among the most important phenomena that control a variety of chemical and biological transformations. Although extensively studied in a variety of natural systems and discrete metal complexes, PCET mechanisms are less well codified in the case of purely organic compounds. Here we report that a planar β,β′- phenylene-bridged hexaphyrin (1.0.1.0.1.0), a 24 π-electron antiaromatic species termed rosarin, displays unique redox reactivity on protonation. Specifically, treatment with acid (for example, HI) yields a 26 π-electron aromatic triprotonated monocationic species that is produced spontaneously via an intermediate - but stable - 25 π-electron non-aromatic triprotonated monoradical dication. This latter species is also produced on treatment of the original 24 π-electron antiaromatic starting material with HCl or HBr. The stepwise nature of the proton-coupled reduction observed in the planar rosarin stands in marked contrast to that seen for non-annulated rosarins and other ostensibly antiaromatic expanded porphyrinoids.",
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Ishida, M, Kim, SJ, Preihs, C, Ohkubo, K, Lim, JM, Lee, BS, Park, JS, Lynch, VM, Roznyatovskiy, VV, Sarma, T, Panda, PK, Lee, CH, Fukuzumi, S, Kim, D & Sessler, JL 2013, 'Protonation-coupled redox reactions in planar antiaromatic meso-pentafluorophenyl-substituted o-phenylene-bridged annulated rosarins', Nature chemistry, vol. 5, no. 1, pp. 15-20. https://doi.org/10.1038/nchem.1501

Protonation-coupled redox reactions in planar antiaromatic meso-pentafluorophenyl-substituted o-phenylene-bridged annulated rosarins. / Ishida, Masatoshi; Kim, Soo Jin; Preihs, Christian; Ohkubo, Kei; Lim, Jong Min; Lee, Byung Sun; Park, Jung Su; Lynch, Vincent M.; Roznyatovskiy, Vladimir V.; Sarma, Tridib; Panda, Pradeepta K.; Lee, Chang Hee; Fukuzumi, Shunichi; Kim, Dongho; Sessler, Jonathan L.

In: Nature chemistry, Vol. 5, No. 1, 01.01.2013, p. 15-20.

Research output: Contribution to journalArticle

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T1 - Protonation-coupled redox reactions in planar antiaromatic meso-pentafluorophenyl-substituted o-phenylene-bridged annulated rosarins

AU - Ishida, Masatoshi

AU - Kim, Soo Jin

AU - Preihs, Christian

AU - Ohkubo, Kei

AU - Lim, Jong Min

AU - Lee, Byung Sun

AU - Park, Jung Su

AU - Lynch, Vincent M.

AU - Roznyatovskiy, Vladimir V.

AU - Sarma, Tridib

AU - Panda, Pradeepta K.

AU - Lee, Chang Hee

AU - Fukuzumi, Shunichi

AU - Kim, Dongho

AU - Sessler, Jonathan L.

PY - 2013/1/1

Y1 - 2013/1/1

N2 - Proton-coupled electron transfer (PCET) processes are among the most important phenomena that control a variety of chemical and biological transformations. Although extensively studied in a variety of natural systems and discrete metal complexes, PCET mechanisms are less well codified in the case of purely organic compounds. Here we report that a planar β,β′- phenylene-bridged hexaphyrin (1.0.1.0.1.0), a 24 π-electron antiaromatic species termed rosarin, displays unique redox reactivity on protonation. Specifically, treatment with acid (for example, HI) yields a 26 π-electron aromatic triprotonated monocationic species that is produced spontaneously via an intermediate - but stable - 25 π-electron non-aromatic triprotonated monoradical dication. This latter species is also produced on treatment of the original 24 π-electron antiaromatic starting material with HCl or HBr. The stepwise nature of the proton-coupled reduction observed in the planar rosarin stands in marked contrast to that seen for non-annulated rosarins and other ostensibly antiaromatic expanded porphyrinoids.

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