RESUMO
Nanocarbons incorporating non-hexagonal aromatic rings - such as five-, seven-, and eight-membered rings - have various intriguing physical properties such as curved structures, unique one-dimensional packing, and promising magnetic, optical, and conductivity properties. Herein, we report an efficient synthetic approach to polycyclic aromatics containing seven-membered rings via a palladium-catalyzed intramolecular Ar-H/Ar-Br coupling. In addition to all-hydrocarbon scaffolds, heteroatom-embedded heptagon-containing polyarenes can be efficiently constructed with this method. Rhodium- and palladium-catalyzed sequential six- and seven-membered ring formations also afford complex heptagon-containing molecular nanocarbons from readily available arylacetylenes and biphenyl boronic acids. Detailed mechanistic analysis by DFT calculations showed the feasibility of seven-membered ring formation by a concerted metalation-deprotonation mechanism. This reaction can serve as a template for the synthesis of a wide range of seven-membered ring-containing molecular nanocarbons.
RESUMO
Molecular nanocarbons containing heptagonal rings have attracted increasing interest due to their dynamic behavior, electronic properties, aromaticity, and solid-state packing. Heptagon incorporation can not only induce negative curvature within nanocarbon scaffolds, but also confer significantly altered properties through interaction with adjacent non-hexagonal rings. Despite the disclosure of several beautiful examples in recent years, synthetic strategies toward heptagon-embedded molecular nanocarbons remain relatively limited due to the intrinsic challenges of heptagon formation and incorporation into polyarene frameworks. In this Review, recent advances in solution-mediated and surface-assisted synthesis of heptagon-containing molecular nanocarbons, as well as the intriguing properties of these frameworks, will be discussed.
