Huang Lin, Wang Qing, Fu Peng, Sun Yuzhu, Xu Jun, Browne Duncan L, Huang Jianhui
School of Pharmaceutical Science and Technology, Tianjin University, Tianjin 300072, P. R. China.
Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, P. R. China.
JACS Au. 2024 Mar 27;4(4):1623-1631. doi: 10.1021/jacsau.4c00105. eCollection 2024 Apr 22.
Reported here is the design and synthesis of a novel class of extended quinolizinium-fused corannulene derivatives with curved geometry. These intriguing molecules were synthesized through a rationally designed synthetic strategy, utilizing double Skraup-Doebner-Von Miller quinoline synthesis and a rhodium-catalyzed C-H activation/annulation (CHAA) as the key steps. Single-crystal X-ray analysis revealed a bowl depth of 1.28-1.50 Å and a unique "windmill-like" shape packing of due to the curvature and incorporation of two aminium ions. All of the newly reported curved salts exhibit green to orange fluorescence with enhanced quantum yields (Φ = 9-13%) and improved dispersibility compared to the pristine corannulene (Φ = 1%). The reduced optical energy gap and lower energy frontier orbital found by doping extended corannulene systems with nitrogen cations was investigated by UV-vis, fluorescence, and theoretical calculations. Electrochemical measurements reveal a greater electron-accepting behavior compared with that of their pyridine analogues. The successful synthesis, isolation, and evaluation of these curved salts provide a fresh perspective and opportunity for the design of cationic nitrogen-doped curved aromatic hydrocarbon-based materials.
本文报道了一类具有弯曲几何结构的新型扩展喹啉鎓稠合碗烯衍生物的设计与合成。这些引人入胜的分子是通过合理设计的合成策略合成的，以双Skraup-Doebner-Von Miller喹啉合成和铑催化的C-H活化/环化（CHAA）为关键步骤。单晶X射线分析表明，由于曲率和两个铵离子的引入，碗深为1.28 - 1.50 Å，且具有独特的“风车状”堆积结构。与原始碗烯（Φ = 1%）相比，所有新报道的弯曲盐均呈现绿色至橙色荧光，量子产率提高（Φ = 9 - 13%）且分散性得到改善。通过紫外可见光谱、荧光光谱和理论计算研究了用氮阳离子掺杂扩展碗烯体系导致的光学能隙减小和前沿轨道能量降低。电化学测量表明，与它们的吡啶类似物相比，这些弯曲盐具有更强的电子接受行为。这些弯曲盐的成功合成、分离和评估为基于阳离子氮掺杂弯曲芳烃的材料设计提供了新的视角和机会。
