Modular Synthesis of Structurally Diverse Azulene‐Embedded Polycyclic Aromatic Hydrocarbons by Knoevenagel‐Type Condensation

The research interest in azulene-embedded polycyclic aromatic hydrocarbons (PAHs) has significantly increased recently, but the lack of efficient synthetic strategies impedes the investigation of their structure-property relationships and further opto-electronic applications. Here we report a modular synthetic strategy towards diverse azulene-embedded PAHs by a tandem Suzuki coupling and base-promoted Knoevenagel-type condensation with good yields and great structural versatility, including non-alternant thiophene-rich PAHs, butterfly- or Z-shaped PAHs bearing two azulene units, and the first example of a two-azulene-embedded double [5]helicene. The structural topology, aromaticity and photophysical properties were investigated by NMR, X-ray crystallography analysis and UV/Vis absorption spectroscopy assisted by DFT calculations. This strategy provides a new platform for rapidly synthesizing unexplored non-alternant PAHs or even graphene nanoribbons with multiple azulene units.