open access

https://hdl.handle.net/2115/95836

Cation‐Stacking Approach Enabling Interconversion between Bis(xanthylium) and its Reduced Species

英語

Redox systems

2024-08-22

Wiley-Blackwell

Chemistry – A European Journal

30(47)

e202401683

Cyclophane-type dications with two units of xanthylium were designed, with the expectation that intramolecular interaction between cation units could induce changes in absorption and redox behavior. The desired dications were synthesized via the macrocyclic diketone as a key intermediate, which was efficiently obtained by a stepwise etherification. X-ray and UV/Vis measurements revealed that the cyclophane-type dications adopt a stacking structure in both the crystal and solution. Due to the intramolecular interaction caused by π-π stacking of the xanthylium units, a considerable blue shift compared to the corresponding monocations and a two-stage one-electron reduction process were observed in the dications. Furthermore, upon electrochemical reduction of dications, the formation of biradicals via radical cation species was demonstrated by UV/Vis spectroscopy with several isosbestic points at both stages. Therefore, the cation-stacking approach is a promising way to provide novel properties due to perturbation of their molecular orbitals and to stabilize the reduced species even though they have open-shell characters.

学術雑誌論文

Accepted Manuscript

This is the peer reviewed version of the following article: Moto Kikuchi, Tomoki Tadokoro, Takuya Tachibana, Shuichi Suzuki, Takanori Suzuki and Yusuke Ishigaki, Chemistry-A European journal Vol.30, e202401683, which has been published in final form at https://doi.org/10.1002/chem.202401683. 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.

0947-6539

1521-3765

AA11076269