A complete experimental and theoretical study has been carried out for aromatic and quinoidal perylene-based bridges, either substituted with bis(diarylamine) or bis(arylimine) groups. The through-bridge inter-redox site electronic couplings (VAB) have been calculated, for their respective mixed-valence radical cation and radical anion species. The unusual similitudes of the resulting VAB values for the given structures reveal the intervention of molecular shapes with balanced semi-quinoidal/semi-aromatic structures in the charge delocalization. An identical molecular object equally responding to the injection of positive or negative charges is rare in the field of organic πconjugated molecules. However, once probed herein for perylene-based systems, it can be extrapolated to others πconjugated bridges. As a result, this work opens the door to the rational design of true ambipolar bulk and molecular conductors.
