open access

https://hdl.handle.net/2115/90710

Geometrical and Electronic Structure of Cation Radical Species of Tetraarylanthraquinodimethane: An Intermediate for Unique Electrochromic Behavior

英語

Electrochromism

2022-11-16

Wiley-Blackwell

Chemistry-an asian journal

17(22)

e202200914

Two tetraarylanthraquinodimethane (Ar(4)AQD) derivatives having two different aryl groups (aminophenyl and methoxyphenyl) were prepared by sequential dibromomethylation and Suzuki-coupling reactions. X-ray analyses showed that they adopt a folded structure in the neutral state whereas the corresponding dications have a planar anthracene ring, to which diarylmethylium units are perpendicularly attached. Different from Ar(4)AQD having the same substituents that undergoes facile two-electron transfer during interconversion with the dicationic state, the intermediary cation radical becomes long-lived in the newly prepared unsymmetric derivatives. The geometric and electronic structures of the open-shell intermediates were elucidated through electrochemical and theoretical investigation, with revealing that the cation radicals adopt the twisted geometry like dications. Upon electrolyses of the dications, the twisted cation radicals were involved in the electrochromism whereas their steady-state concentration is negligible in the oxidation process, thus realizing unique tricolor electrochromic behavior with a hysteretic pattern of color change (colorless -> purple -> blue -> colorless).

学術雑誌論文

Accepted Manuscript

This is the peer reviewed version of the following article: Y. Ishigaki, R. Fukagawa, K. Sugawara, T. Harimoto, T. Suzuki, Chem. Asian J. 2022, 17, e202200914., which has been published in final form at https://doi.org/10.1002/asia.202200914. 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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