Buckybowls, bowl-shaped polycyclic aromatic hydrocarbons structurally related to fullerenes, represent a class of hydrocarbons with unique properties and a potential for application as novel materials. This review outlines the development of the practical preparations of buckybowls, starting with the original synthesis of corannulene achieved in 1966. A particular attention is paid to the last decade developments which include construction of large, highly nonplanar molecular networks (molecular clips and tweezers) capable of binding guest molecules of various sizes and shapes. In particular, such molecular clips were proven to form stable supramolecular complexes with fullerenes C₆₀ and C₇₀, both in solution and in the solid state.

Palladium-catalyzed cyclotrimerization of corannulyne generated from 2-trimethylsilylcorannulenyl triflate produced a C₆₀H₂₄ hydrocarbon that prefers a highly nonplanar “twist” conformation of C₁ symmetry, as demonstrated by X-ray crystal structure determination and HDFT calculations. Its three corannulene subunits, identical in the idealized D_3h symmetry, exhibit dramatically different inversion barriers (from 8.4 to 17.3 kcal mol^–1), tuned by the steric congestion inside the highly dissymmetric structure. Bowl-to-bowl inversion of the corannulene unit with the lowest activation barrier results in pseudorotation of the molecule and gives rise to a ¹H NMR spectrum exhibiting only 12 distinct proton signals. The line-shape analysis of selected NMR signals gave an estimation of the barrier at 8.5–8.6 kcal mol^–1.