Laboratory for Computational Molecular Design, Institute of Chemical Sciences and Engineering, École Polytechnique Fedéralé de Lausanne (EPFL), 1015, Lausanne, Switzerland.
Angew Chem Int Ed Engl. 2023 Apr 3;62(15):e202218156. doi: 10.1002/anie.202218156. Epub 2023 Mar 3.
Molecules with inversion of the singlet and triplet excited-state energies are highly promising for the development of organic light-emitting diodes (OLEDs). To date, azaphenalenes are the only class of molecules where these inversions have been identified. Here, we screen a curated database of organic crystal structures to identify existing compounds for violations of Hund's rule in the lowest excited states. We identify two further classes with this behavior. The first, a class of zwitterions, has limited relevance to molecular emitters as the singlet-triplet inversions occur in the third excited singlet state. The second class consists of two D -symmetry non-alternant hydrocarbons, a fused azulene dimer and a bicalicene, whose lowest excited singlet states violate Hund's rule. Due to the connectivity of the polycyclic structure, they achieve this symmetry through aromatic stabilization. These hydrocarbons show promise as the next generation of building blocks for OLED emitters.
分子的单重态和三重态激发态能量反转对于开发有机发光二极管(OLED)非常有前景。迄今为止,吖啶是唯一一类已确定存在这些反转的分子。在这里,我们筛选了一个经过精心整理的有机晶体结构数据库,以确定现有的化合物是否违反了最低激发态中的洪德规则。我们确定了另外两类具有这种行为的化合物。第一类,两性离子,由于单重态-三重态反转发生在第三激发单线态中,因此与分子发射器的相关性有限。第二类由两个 D 对称非交替烃组成,一个稠合的薁二聚体和一个双环烯,其最低激发单线态违反了洪德规则。由于多环结构的连通性,它们通过芳香稳定化达到这种对称性。这些碳氢化合物有望成为下一代 OLED 发射器的构建块。