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Efficient room-temperature synthesis of a highly strained carbon nanohoop fragment of buckminsterfullerene

Nature Chemistry volume 6, pages 404–408 (2014)Cite this article

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Abstract

Warped carbon-rich molecules have captured the imagination of scientists across many disciplines. Owing to their promising materials properties and challenging synthesis, strained hydrocarbons are attractive targets that push the limits of synthetic methods and molecular design. Herein we report the synthesis and characterization of [5]cycloparaphenylene ([5]CPP), a carbon nanohoop that can be envisaged as an open tubular fragment of C60, the equator of C70 fullerene and the unit cycle of a [5,5] armchair carbon nanotube. Given its calculated 119 kcal mol−1 strain energy and severely distorted benzene rings, this synthesis, which employs a room-temperature macrocyclization of a diboronate precursor, single-electron reduction and elimination, is remarkably mild and high yielding (27% over three steps). Single-crystal X-ray diffraction data were obtained to confirm its geometry and previously disputed benzenoid character. First and second pseudoreversible oxidation and reduction events were observed via cyclic voltammetry. The ease of synthesis, high solubility and narrowest optical HOMO/LUMO gap of any para-polyphenylene synthesized make [5]CPP a desirable new material for organic electronics.

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Figure 1: Prototypical distressed hydrocarbons that have succumbed to rational organic synthesis.
Figure 2: A rapid synthetic route to [5]CPP.
Figure 3: Analysis of [5]CPP by X-ray diffraction crystallography.
Figure 4: Ultraviolet–visible absorbance data for [5]CPP.
Figure 5: Cyclic voltammetry of [5]CPP in THF.

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Acknowledgements

This work was supported by a National Science Foundation CAREER award (CHE-1255219), an Alfred P. Sloan Research Fellowship and a Boston University Ignition Award. The authors gratefully acknowledge J. Bacon (Boston University) for crystal-structure determination.

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  1. Paul J. Evans and Evan R. Darzi: These authors contributed equally

Authors and Affiliations

  1. Department of Chemistry and Division of Materials Science and Engineering, Boston University, Boston, 02215, Massachusetts, USA

    Paul J. Evans, Evan R. Darzi & Ramesh Jasti

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Contributions

E.R.D. and P.J.E. conceived the project, designed and carried out the experiments, performed the calculations, analysed the data and wrote the manuscript with equal contribution. As such, E.R.D. and P.J.E. are credited as co-first authors. R.J. played a critical role in discussion of the experimental design, project direction, experiments and results, and preparation of the manuscript.

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Correspondence to Ramesh Jasti.

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The authors declare no competing financial interests.

Supplementary information

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Supplementary information (PDF 1955 kb)

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Crystallographic data for compound 3 (CIF 1175 kb)

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Crystallographic data for compound [5]CPP (CIF 132 kb)

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Evans, P., Darzi, E. & Jasti, R. Efficient room-temperature synthesis of a highly strained carbon nanohoop fragment of buckminsterfullerene. Nature Chem 6, 404–408 (2014). https://doi.org/10.1038/nchem.1888

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