Lemniscular [16]Cycloparaphenylene: A Radially Conjugated Figure-Eight Aromatic Molecule

Kabali Senthilkumar, Mateusz Kondratowicz, Tadeusz Lis, Piotr J. Chmielewski, Joanna Cybińska, José L. Zafra, Juan Casado, Thomas Vivès, Jeanne Crassous, Ludovic Favereau,

Journal of the American Chemical Society · 2019 · 205 citations · 49 references

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Abstract

A cycloparaphenylene-based molecular lemniscate (CPPL) was obtained in a short synthesis involving masked p-phenylene equivalents. The strained figure-eight geometry of CPPL is sustained by the incorporated 9,9'-bicarbazole subunit, which also acts as a stereogenic element. The shape of the distorted [16]cycloparaphenylene nanohoop embedded in CPPL is accurately approximated with a Booth lemniscate. The structure of CPPL, investigated using NMR and Raman spectroscopic methods, revealed strain-dependent features, consistent with the variable curvature of the ring. The electronic and optical properties of CPPL combine features more characteristic of smaller cycloparaphenylenes, such as a reduced optical bandgap and red-shifted fluorescence. CPPL was resolved into enantiomers, which are configurationally stable and provide strong chiroptical responses, including circularly polarized luminescence.

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