Department of Chemistry, Marquette University, P.O. Box 1881, Milwaukee, WI 53201-1881 (USA).
Angew Chem Int Ed Engl. 2015 Nov 23;54(48):14468-72. doi: 10.1002/anie.201506402. Epub 2015 Oct 1.
Triptycenes spontaneously assemble into two-dimensional networks in which long-range charge transport is facilitated by the extensive electronic coupling through the triptycene framework (intramolecularly) and by cofacial π-stacking (intermolecularly). While designing and synthesizing next-generation triptycenes containing polyaromatic chromophores, the electronic coupling amongst the chromophores was observed to be highly dependent on the nature and position of the substituents. Herein, we demonstrate using hexaalkoxytriptycenes that the electronic coupling amongst the chromophores is switched on and off by a simple repositioning of the substituents, which alters the nodal arrangement of the HOMOs of the individual chromophores. A visual inspection of the HOMOs can thus provide a ready evaluation of the electronic coupling in polychromophoric molecules/assemblies, and will serve as an important tool for the rational design of modern charge-transport materials.
三并苯会自发组装成二维网络，其中通过三并苯骨架（分子内）和面对面的π-堆积（分子间）的广泛电子耦合促进长程电荷传输。在设计和合成含有多芳族生色团的新一代三并苯时，观察到生色团之间的电子耦合高度依赖于取代基的性质和位置。在此，我们使用六烷氧基三并苯证明，通过简单地重新定位取代基可以打开和关闭生色团之间的电子耦合，这会改变各个生色团 HOMO 的节点排列。因此，对 HOMO 的直观检查可以为多生色团分子/组装体中的电子耦合提供快速评估，并将成为现代电荷传输材料合理设计的重要工具。
