open access

https://hdl.handle.net/2115/93596

Domino-Redox Reaction Induced by An Electrochemically Triggered Conformational Change

英語

X-Ray Diffraction

2024-01-02

Wiley-Blackwell

Angewandte chemie-international edition

63(1)

e202316753

The concept of a domino-type reaction has been applied in a wide range of fields such as synthetic organic chemistry, material engineering, and life science. To extend the domino concept to redox chemistry, we designed and synthesized a dimeric quinodimethane (QD) with a nonplanar dithiin spacer. The domino-redox properties can be activated by raising the temperature, based on a thermally equilibrated twisted conformation of QD, which has a higher HOMO level that is more readily oxidized. After one QD unit is oxidized (trigger), steric repulsion and electronic interaction between electrophores make the neighboring QD unit adopt a twisted conformation (domino process), which facilitates the following oxidation. Thus, a domino-redox reaction was achieved for the first time by a change in the HOMO level due to a drastic change in the molecular conformation. A thermally activated twisted-folded (T-F) form of bisquinodimethane with a dithiin skeleton (SS-BQD) undergoes a facile apparent 2e-transfer (trigger). Furthermore, in the resulting dication, the steric repulsion and interelectrophore interaction cause a facile and rapid change in the structure from the as-generated T2+-F form to the T2+-T form (domino), which facilitates the subsequent oxidation to the tetracation (domino).image

学術雑誌論文

Accepted Manuscript

This is the peer reviewed version of the following article : Angewandte chemie international edition Vol.63(1), which has been published in final form at https://doi.org/10.1002/anie.202316753. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited.

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