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Dibenzotropylium-Capped Orthogonal Geometry Enabling Isolation and Examination of a Series of Hydrocarbons with Multiple 14x-Aromatic Units

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Title: Dibenzotropylium-Capped Orthogonal Geometry Enabling Isolation and Examination of a Series of Hydrocarbons with Multiple 14x-Aromatic Units
Authors: Hayashi, Yuki Browse this author
Suzuki, Shuichi Browse this author
Suzuki, Takanori Browse this author
Ishigaki, Yusuke Browse this author →KAKEN DB
Issue Date: 1-Feb-2023
Publisher: American Chemical Society
Journal Title: Journal of the American Chemical Society
Volume: 145
Issue: 4
Start Page: 2596
End Page: 2608
Publisher DOI: 10.1021/jacs.2c12574
Abstract: A series of six dications composed of pure hydrocarbons with one to six non-substituted 9,10-anthrylene units end-capped with two dibenzotropyliums were designed and synthesized to elucidate the electronic properties of huge oligo(9,10-anthrylene) backbones. Their structures were success-fully determined by X-ray analyses even in the case of eight planar 14 pi-electron units, revealing that all dications adopt almost orthogonally twisted structures between neighboring units. Spectroscopic and voltammetric analyses show that neither the significant overlap of orbitals nor the delocalization of electrons between 14 pi-electron units occurs due to the orthogonally twisted geometry even in solution. As a result, sequential oxidation processes were observed with the reversible formation of multivalent cations with the release of the same number of electrons as the number of anthrylene units. Upon two-electron reduction, a closed-shell butterfly-shaped form was obtained from the dication containing one anthrylene unit, whereas open-shell twisted biradicals were isolated as stable entities in the cases of derivatives containing three to six anthrylene units. Notably, from the derivative with two anthrylene units, a metastable open-shell isomer was obtained quantitatively and underwent slow thermal conversion to the most stable closed-shell isomer (Ea = 23.1 kcal mol-1). There is a drastic change in oxidation potentials between two neutral species (OLE = 1.32 V in CH2Cl2). Since the present dications were regenerated upon oxidation of the isolated reduction products, these systems may contribute to the development of advanced response systems capable of switching color, magnetic properties, and oxidative properties by using a cation-capped orthogonal geometry.
Type: article
Appears in Collections:理学院・理学研究院 (Graduate School of Science / Faculty of Science) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)

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