About Perfluoropolyhedranes, Their Electron-Accepting Ability and Questionable Supramolecular Hosting Capacity

Polyhedral molecules are appealing for their eye-catching architecture and distinctive chemistry. Perfluorination of such, often greatly strained, compounds is a momentous challenge. It drastically changes the electron distribution, structure and properties. Notably, small high-symmetry perfluoropolyhedranes feature a centrally located, star-shaped low-energy unoccupied molecular orbital that can host an extra electron within the polyhedral frame, thus producing a radical anion, without loss of symmetry. This predicted electron-hosting capacity was definitively established for perfluorocubane, the first perfluorinated Platonic polyhedrane to be isolated pure. Hosting atoms, molecules, or ions in such cage structures is, however, all but forthright, if not illusionary, offering no easy access to supramolecular constructs. While adamantane and cubane have fostered numerous applications in materials science, medicine, and biology, specific uses for their perfluorinated counterparts remain to be established. Some aspects of highly fluorinated carbon allotropes, such as fullerenes and graphite, are briefly mentioned for context.

Automated summary

Polyhedral molecules are attractive due to their unique architecture and chemistry. Perfluorination of these compounds, which are often highly strained, poses a significant challenge as it profoundly alters their electron distribution, structure, and properties. Specifically, small high-symmetry perfluoropolyhedranes have been found to possess a centrally located, star-shaped low-energy unoccupied molecular orbital that can accommodate an extra electron, resulting in a radical anion without symmetry loss. The ability to host atoms, molecules, or ions within these cage structures is complicated, and the specific applications of perfluorinated counterparts of adamantane and cubane are yet to be determined. Some aspects of highly fluorinated carbon allotropes, such as fullerenes and graphite, are mentioned briefly for context.