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

Nature Chemistry volume 5, pages 15–20 (2013)Cite this article

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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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Figure 1: Conformational restriction of rosarin derivatives by β,β′-phenylene bridges gives the planar 24 π-electron conjugated porphyrinoid 1.
Figure 2: Molecular structures derived from X-ray crystallographic analyses and partial 1H NMR spectra.
Figure 3: Steady-state absorption spectra of compounds 1 (black line), H31·Cl2• (red line) and H31·Cl (blue line) in CH2Cl2.
Figure 4: Cyclic voltammetry (CV) showing the protonation-induced reduction potential shifts.
Figure 5: Redox reaction cycle of 1 and reversible protonation–deprotonation pathways of 2 observed in the presence of protic acids and an organic base.

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Acknowledgements

Support is acknowledged from the US National Science Foundation (CHE-1057904 to J.L.S.), the Robert A. Welch Foundation (F-1018 to J.L.S.), Grant-in-Aid (No. 20108010 to S.F. and 23750014 to K.O.) from the Ministry of Education, Culture, Sports, Science and Technology, Japan, the World Class University Program (R32-2010-000-10217-0 to D.K. and R31-2008-000-10010-0 to S.F.) of the Ministry of Education, Science and Technology, the Basic Science Research Programs, National Research Foundation (2009-0087013 to C-H.L), BK21, Council of Scientific and Industrial Research, India (from a senior research fellowship to T.S.) and the Department of Science and Technology India (SR/S1/IC-20/2007 to P.K.P.).

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Authors and Affiliations

  1. Department of Chemistry, Yonsei University, Seoul, 120-749, Korea

    Masatoshi Ishida, Jong Min Lim, Byung Sun Lee, Dongho Kim & Jonathan L. Sessler

  2. Department of Chemistry, Kangwon National University, Chun-chon, 200-701, Korea

    Soo-Jin Kim & Chang-Hee Lee

  3. Department of Chemistry & Biochemistry, The University of Texas, Austin, 78712-0165, Texas, USA

    Christian Preihs, Jung Su Park, Vincent M. Lynch, Vladimir V. Roznyatovskiy & Jonathan L. Sessler

  4. Department of Material and Life Science, Graduate School of Engineering, Osaka University, ALCA, Japan Science and Technology Agency, Suita, 565-0871, Osaka, Japan

    Kei Ohkubo & Shunichi Fukuzumi

  5. School of Chemistry, University of Hyderabad, Hyderabad, India

    Tridib Sarma & Pradeepta K. Panda

  6. Department of Bioinspired Science, Ewha Womans University, Seoul, 120-750, Korea

    Shunichi Fukuzumi

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Contributions

J.L.S. supervised the project. M.I. designed and carried out the bulk of the experimental and theoretical work. S-J.K., C.P., V.V.R., T.S. and P.K.P. performed the syntheses. K.O. carried out the EPR experiment. J.M.L. carried out TA experiments. B.S.L. carried out two photon-absorption experiments. C.P., V.M.L. and J.S.P. carried out X-ray diffraction analyses on the crystals. M.I., C-H.L., S.F., D.K. and J.L.S. co-wrote the paper. All authors contributed to discussions.

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Correspondence to Chang-Hee Lee, Shunichi Fukuzumi, Dongho Kim or Jonathan L. Sessler.

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The authors declare no competing financial interests.

Supplementary information

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Supplementary information (PDF 6972 kb)

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Crystallographic data for compound 1. (CIF 38 kb)

Supplementary information

Crystallographic data for compound H31·Cl. (CIF 38 kb)

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Ishida, M., Kim, SJ., Preihs, C. et al. Protonation-coupled redox reactions in planar antiaromatic meso-pentafluorophenyl-substituted o-phenylene-bridged annulated rosarins. Nature Chem 5, 15–20 (2013). https://doi.org/10.1038/nchem.1501

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