[structure: see text] Polyenyne macrocycles with pi-extended [9]- and [12]radialene frameworks have been synthesized. These radialenes exhibit restricted rotation of the aromatic rings, and the D3- and D4-symmetric structures in solutions have been determined by dynamic NMR. The macrocyclic radialenes bear small to medium inner cavities, and the small cavity of the pi-extended [9]radialene can incorporate a silver cation.
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