Synthesis and Structural Elucidation of Bisdibenzocorannulene in Multiple Redox States

Autor: Chenxin Yang, Sheng Xie, Wangwang Peng, Huiping Xiao, Bo Li, Xinhao Wang, Jishan Wu, Shenglian Luo, Guangwu Li, Zebing Zeng
Rok vydání: 2021
Předmět:
Zdroj: Angewandte Chemie International Edition. 60:19790-19796
ISSN: 1521-3773
1433-7851
Popis: We report an anti-folded bowl-shaped bisdibenzocorannulene (BDBC) featuring a new chair-cyclohexane-like hexagon as a bridge of two dibenzocorannulene moieties. The neutral compound showed multiple redox-active properties and could be converted to the corresponding redox states through chemical reduction or oxidation. Chemical reduction of BDBC by stoichiometric addition of metallic potassium in the presence of [18]crown-6 ether, provided a radical anion BDBC.- and a dianion BDBC2- , respectively; while chemical oxidation by silver hexafluoroantimonate(V), converted the neutral compound to an open-shell singlet diradical dication (BDBC.. )2+ . The structural consequences of both electron-reduction and oxidation were closely related to the release of ring-strain of the bowl-shaped π-scaffold and imposed steric hindrance of the hexagonal bridge. In addition, the unusual open-shell nature of the dication could mainly be attributed to the changing of localized antiaromaticity in the closed-shell structure to delocalized character in the biradical, and thus the emergence of weakly bonded π-electrons.
Databáze: OpenAIRE
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