Abstract Syntheses of large polycyclic aromatic hydrocarbons (PAHs) and graphene nanostructures demand methods that are capable of selectively and efficiently fusing large numbers of aromatic rings, yet such methods remain scarce. Herein, we report a new approach that is based on the quantitative intramolecular reductive cyclization of an oligo(diyne) with a low‐valent zirconocene reagent, which gives a PAH with one or more annulated zirconacyclopentadienes (ZrPAHs). The efficiency of this process is demonstrated by a high‐yielding fivefold intramolecular coupling to form a helical ZrPAH with 16 fused rings (from a precursor with no fused rings). Several other PAH topologies are also reported. Protodemetalation of the ZrPAHs allowed full characterization (including by X‐ray crystallography) of PAHs containing one or more appended dienes with the ortho‐quinodimethane (o‐QDM) structure, which are usually too reactive for isolation and are potentially valuable for the fusion of additional rings by Diels–Alder reactions.
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