Synthesis and Characterization of Quinoxaline-Fused Cyclopenta[cd]azulene

Azulene-based polycyclic hydrocarbons have garnered much attention as potential materials for organic optoelectronic devices and as molecular models for graphene nanosheets with structural defects. Although various methods for ring fusions to an azulene core have been established for ring fusions to an azulene core, efficient synthetic methodologies for ortho- and peri-fusion to an azulene core are still lacking, which hinders the investigation of the effect of the ortho- and peri-fusion on the electronic properties of the embedded azulene core. Herein, we describe the synthesis and characterization of quinoxaline-fused cyclopenta[cd]azulene 4 as a new ortho- and peri-fused azulene derivative. The target molecule 4 was successfully synthesized in four steps from 4-methylazulene. The ring annulation decreased the lowest excitation energy compared with that of azulene and its structural isomer 5 and led to multiple reversible reduction processes. Characterization of the molecular geometry and optoelectronic properties of 4 revealed that the embedded azulene core preserves its original aromaticity, while the fused quinoxaline acts as a nucleophilic and basic site. These features suggest that 4 could serve as a metal ligand, a near-infrared absorber, and a component in organic functional devices.