Synthesis and Structural Elucidation of Bisdibenzocorannulene in Multiple Redox States

Abstract

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 BDBC^2- , 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.

Keywords: curved polycyclic hydrocarbons; open-shell ions; pi-extension; redox states; structure elucidation.