Aromaticity Relocation in Perylene Derivatives upon Two-Electron Oxidation To Form Anthracene and Phenanthrene

We prepared perylene dications 12+ and 22+ by using "capped" perylene derivatives, and for the first time, successfully obtained single crystals of a perylene dication 12+ that enabled us to perform its structural analysis. We realized that the substituted aryl groups on perylene control the positions of positive charges, thus the remaining electronic system satisfies Clar's sextet rule toward the highest number of localized sextets. Experimental and theoretical evidence proved that Clar's aromatic π-sextet rule could be applied even for the dicationic perylenes in a very simple way.