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

Abstract

AbstractThe 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.