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
Department of Molecular Nanoscience and Organic Materials, Institut de Ciència de Materials de Barcelona (ICMAB)/ CIBER-BBN, Campus Universitari de Bellaterra., 08193, Cerdanyola, Spain.
Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543, Singapore, Singapore.
Angew Chem Int Ed Engl. 2019 Oct 7;58(41):14467-14471. doi: 10.1002/anie.201905657. Epub 2019 Aug 27.
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 ) have been calculated for their respective mixed-valence radical cation and radical anion species. The unusual similitudes of the resulting V 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.
分别对用双（二芳基胺）和双（芳基亚胺）基团取代的基于苝的芳香族和醌型桥进行了完整的实验和理论研究。已针对其各自的混合价自由基阳离子和自由基阴离子物种计算了跨桥氧化还原位点间的电子耦合（V）。给定结构的所得V值的异常相似性揭示了具有平衡半醌型/半芳香结构的分子形状在电荷离域中的干预。在有机π共轭分子领域中，一个相同的分子对象对正电荷或负电荷的注入有相同响应的情况很少见。然而，一旦在本文中对基于苝的体系进行了探究，就可以推断到其他π共轭桥。因此，这项工作为真正的双极性块状和分子导体的合理设计打开了大门。
