Extended Quinolizinium-Fused Corannulene Derivatives: Synthesis and Properties.

Abstract

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 12a(2PF6-) 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 (Φf = 9-13%) and improved dispersibility compared to the pristine corannulene (Φf = 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.