Get access

A Triphenylamine Double-Decker: From a Delocalized Radical Cation to a Diradical Dication with an Excited Triplet State

Authors

  • Yuichiro Yokoyama,

    1. Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510 (Japan)
    Search for more papers by this author
  • Daisuke Sakamaki,

    1. Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510 (Japan)
    Search for more papers by this author
  • Dr. Akihiro Ito,

    Corresponding author
    1. Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510 (Japan)
    • Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510 (Japan)
    Search for more papers by this author
  • Prof. Dr. Kazuyoshi Tanaka,

    1. Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510 (Japan)
    Search for more papers by this author
  • Dr. Motoo Shiro

    1. Rigaku Corporation, X-ray Research Laboratory, Matsubaracho 3-9-12, Akishima, Tokyo, 196-8666 (Japan)
    Search for more papers by this author

  • The present work was supported by Grant-in-Aid for Scientific Research (B) (20350065) from the Japan Society for the Promotion of Science (JSPS). D.S. thanks the JSPS Research Fellowship for Young Scientists.

Abstract

original image

The redox properties and electronic structures of polycationic species were examined using a triphenylamine double-decker species. The double-decker has a strong electron-donating ability, and the spin in the radical cation is delocalized over the whole caged skeleton, despite no direct transannular π–π interaction between two TPA decks. Moreover, the diradical dication has spin-singlet character, despite the meta-phenylene linkage.

Ancillary