π‐Extended Dihydrophenazines with Three‐State NIR Electrochromism Involving Large Conformational Changes

  • Juri Nagasaki
    Department of Molecular and Macromolecular Chemistry Graduate School of Engineering Nagoya University, Furo-cho, Chikusa-ku Nagoya Aichi 464-8603 Japan
  • Satoru Hiroto
    Department of Molecular and Macromolecular Chemistry Graduate School of Engineering Nagoya University, Furo-cho, Chikusa-ku Nagoya Aichi 464-8603 Japan
  • Hiroshi Shinokubo
    Department of Molecular and Macromolecular Chemistry Graduate School of Engineering Nagoya University, Furo-cho, Chikusa-ku Nagoya Aichi 464-8603 Japan

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<jats:title>Abstract</jats:title><jats:p>π‐Extended dihydrophenazines were successfully prepared by oxidation of 2‐(<jats:italic>N</jats:italic>‐arylamino)anthracenes. Their roof‐type conformations were revealed by X‐ray diffraction analysis, and the analysis of the optical properties indicated the presence of intramolecular charge‐transfer processes. Upon chemical oxidation, the electronic absorption dramatically changed in a two‐step fashion. The electron spin resonance (ESR) analysis revealed that, depending on the amount of oxidant added, either a paramagnetic radical cation or a diamagnetic dication was generated. The NMR analysis revealed a conformational change upon oxidation, which was supported by theoretical calculations. A three‐state electrochromic behavior was observed during the electrochemical oxidation and reduction cycles, showing sequential switching between visible and near‐infrared (NIR) absorption properties upon application of electrochemical stimuli.</jats:p>

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