Perylene π‐Bridges Equally Delocalize Anions and Cations: Proportioned Quinoidal and Aromatic Content. (27th August 2019)

• Record Type: Journal Article
• Authors: Mayorga Burrezo, Paula; Zeng, Wangdong; Moos, Michael; Holzapfel, Marco; Canola, Sofia; Negri, Fabrizia; Rovira, Concepciò; Veciana, Jaume; Phan, Hoa; Wu, Jishan; Lambert, Christoph; Casado, Juan
• Is Part Of: Angewandte Chemie. Volume 131:Number 41(2019)
• Page Start: 14609
• Page End: 14613
• Publication Date: 2019-08-27
• Subjects: Aromatizität -- Konjugation -- Radikale -- Redoxchemie -- Strukturaufklärung; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201905657
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: A complete experimental and theoretical study has been carried out for aromatic and quinoidal perylene‐based bridges substituted with bis(diarylamine) and bis(arylimine) groups respectively. The through‐bridge inter‐redox site electronic couplings ( V AB ) have been calculated for their respective mixed‐valence radical cation and radical anion species. The unusual similitudes of the resulting V AB 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 either positive or negative charges is rare in the field of organic π‐conjugated molecules. However, once probed herein for perylene‐based systems, it can be extrapolated to other π‐conjugated bridges. As a result, this work opens the door to the rational design of true ambipolar bulk and molecular conductors. Abstract : Gleich mit unterschiedlicher Ladung : Aromatische und chinoide Brücken auf Perylenbasis, die mit Bis(diarylamin)‐ bzw. Bis(arylimin)‐Gruppen substituiert sind, wurden experimentell und theoretisch studiert. Entfernung oder Einführung eines Elektrons führen zu einem Kation bzw. Anion mit bemerkenswert ähnlichen Eigenschaften.