Perfluorocycloparaphenylenes

Synthetic methods for the preparation of perfluorinated aromatic compounds are desirable in materials science. Here, the authors synthesize perfluorocycloparaphenylenes, fully fluorinated carbon nanorings, through a nickel-mediated one-pot method. Perfluorinated aromatic compounds, the so-called perfluoroarenes, are widely used in materials science owing to their high electron affinity and characteristic intermolecular interactions. However, methods to synthesize highly strained perfluoroarenes are limited, which greatly limits their structural diversity. Herein, we report the synthesis and isolation of perfluorocycloparaphenylenes (PFCPPs) as a class of ring-shaped perfluoroarenes. Using macrocyclic nickel complexes, we succeeded in synthesizing PF[n]CPPs (n = 10, 12, 14, 16) in one-pot without noble metals. The molecular structures of PF[n]CPPs (n = 10, 12, 14) were determined by X-ray crystallography to confirm their tubular alignment. Photophysical and electrochemical measurements revealed that PF[n]CPPs (n = 10, 12, 14) exhibited wide HOMO-LUMO gaps, high reduction potentials, and strong phosphorescence at low temperature. PFCPPs are not only useful as electron-accepting organic materials but can also be used for accelerating the creation of topologically unique molecular nanocarbon materials.

Automated summary

In this study, perfluorocycloparaphenylenes (PFCPPs), a class of ring-shaped perfluoroarenes, were synthesized through a one-pot method using macrocyclic nickel complexes. The molecular structures and properties of the synthesized PFCPPs were confirmed, and they were found to have wide HOMO-LUMO gaps, high reduction potentials, and strong phosphorescence at low temperature. PFCPPs have potential applications as electron-accepting organic materials and for creating topologically unique molecular nanocarbon materials.