Sumanenetrione Anions Generated by Electrochemical and Chemical Reduction

• Shuhei Higashibayashi

  Department of Functional Molecular Science, School of Physical Sciences, The Graduate University for Advanced Studies

• Binod Babu Shrestha

  Department of Functional Molecular Science, School of Physical Sciences, The Graduate University for Advanced Studies

• Yuki Morita

  Research Center of Integrative Molecular Systems, Institute for Molecular Science

• Masahiro Ehara

  Department of Theoretical and Computational Molecular Science, Institute for Molecular Science

• Kei Ohkubo

  Department of Material and Life Science, Graduate School of Engineering, Osaka University

• Shunichi Fukuzumi

  Department of Material and Life Science, Graduate School of Engineering, Osaka University

• Hidehiro Sakurai

  Department of Functional Molecular Science, School of Physical Sciences, The Graduate University for Advanced Studies

抄録

The electrochemical reduction of sumanenetrione by cyclic voltammetry showed stepwise multielectron reduction. Cyclic voltammograms of the stepwise first and second one-electron reduction exhibited reversible waves with associated reduction potentials that were almost equivalent to those of C60. EPR studies of the chemically generated monoanion and dianion of sumanenetrione, in conjunction with theoretical calculations, revealed their structures. The radical anion exhibited C3v symmetric spin delocalization over the entire bowl structure. The radical anion exhibited several absorption bands covering the whole visible to near-IR region. The nature of excitations was assigned by SAC/SAC-CI SD-R calculations. The dianion has a singlet ground state with a large energy gap between the singlet and triplet states. The dianion, too, has C3v symmetry with delocalization over the bowl structure. The major contributing structure of the dianion is the closed-shell configuration rather than the open-shell biradical configuration.

収録刊行物

• Chemistry Letters

  Chemistry Letters 43 (8), 1297-1299, 2014-05-10

  Oxford University Press (OUP)

キーワード

• General Chemistry

詳細情報

• CRID: 1360846644035676928
• NII論文ID: 130004427150
• DOI: 10.1246/cl.140351
• ISSN: 13480715
• ISSN: 03667022
• Web Site: https://academic.oup.com/chemlett/article-pdf/43/8/1297/55641062/cl.140351.pdf
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