Hecht Markus, Schlossarek Tim, Stolte Matthias, Lehmann Matthias, Würthner Frank
Institut für Organische Chemie, Center for Nanosystems Chemistry & Bavarian Polymer Institute, Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
Angew Chem Int Ed Engl. 2019 Sep 9;58(37):12979-12983. doi: 10.1002/anie.201904789. Epub 2019 Jul 19.
A novel core-shell structured columnar liquid crystal composed of a donor-acceptor dyad of tetraphenoxy perylene bisimide (PBI), decorated with four bithiophene units on the periphery, was synthesized. This molecule self-assembles in solution into helical J-aggregates guided by π-π interactions and hydrogen bonds which organize into a liquid-crystalline (LC) columnar hexagonal domain in the solid state. Donor and acceptor moieties exhibit contrasting exciton coupling behavior with the PBIs' (J-type) transition dipole moment parallel and the bithiophene side arms' (H-type) perpendicular to the columnar axis. The dyad shows efficient energy and electron transfer in solution as well as in the solid state. The synergy of photoinduced electron transfer (PET) and charge transport along the narcissistically self-assembled core-shell structure enables the implementation of the dye in two-contact photoconductivity devices giving rise to a 20-fold increased photoresponse compared to a reference dye without bithiophene donor moieties.
合成了一种新型的核壳结构柱状液晶，它由四苯氧基苝二酰亚胺（PBI）的供体-受体二元体系组成，其外围装饰有四个联噻吩单元。该分子在溶液中通过π-π相互作用和氢键自组装成螺旋J-聚集体，这些相互作用在固态下组织成液晶（LC）柱状六方域。供体和受体部分表现出对比鲜明的激子耦合行为，PBI的（J型）跃迁偶极矩与柱状轴平行，联噻吩侧臂的（H型）跃迁偶极矩与柱状轴垂直。该二元体系在溶液和固态中均表现出高效的能量和电子转移。光致电子转移（PET）与沿自恋自组装核壳结构的电荷传输之间的协同作用，使得该染料能够应用于双接触光电导器件中，与没有联噻吩供体部分的参比染料相比，其光响应提高了20倍。
