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Synthesis of polyynes to model the sp-carbon allotrope carbyne

Nature Chemistry volume 2, pages 967–971 (2010)Cite this article

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Abstract

Carbyne is an allotrope of carbon composed of sp-hybridized carbon atoms. Although its formation in the laboratory is suggested, no well-defined sample is described. Interest in carbyne and its potential properties remains intense because of, at least in part, technological breakthroughs offered by other carbon allotropes, such as fullerenes, carbon nanotubes and graphene. Here, we describe the synthesis of a series of conjugated polyynes as models for carbyne. The longest of the series consists of 44 contiguous acetylenic carbons, and it maintains a framework clearly composed of alternating single and triple bonds. Spectroscopic analyses for these polyynes reveal a distinct trend towards a finite gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital for carbyne, which is estimated to be ∼485 nm (∼2.56 eV). Even the longest members of this series of polyynes are not particularly sensitive to light, moisture or oxygen, and they can be handled and characterized under normal laboratory conditions.

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Figure 1
Figure 2: Spectroscopic and crystallographic characterization of polyynes 1a–1j.

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Acknowledgements

This work was supported by the University of Alberta and the Natural Sciences and Engineering Research Council of Canada (NSERC) through the Discovery Grant program. W.A.C. thanks the NSERC (Postgraduate Scholarship-D) and the Alberta Ingenuity Fund for scholarship support. We also thank F. Marsiglio for discussions and M. Ferguson and R. McDonald for solving the X-ray structures for 4f and 1b, respectively.

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Author notes

  1. Rik R. Tykwinski

    Present address: Present address: Institut für Organische Chemie, Friedrich-Alexander-Universität, Erlangen-Nürnberg, Henkestrasse 42, 91054 Erlangen, Germany,

Authors and Affiliations

  1. Department of Chemistry, University of Alberta, Edmonton, T6G 2G2, Alberta, Canada

    Wesley A. Chalifoux

  2. Rik R. Tykwinski

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  1. Wesley A. Chalifoux
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Contributions

W.A.C. designed the experiments, and performed the syntheses, characterization and property studies. W.A.C. and R.R.T co-wrote the paper. R.R.T conceived the project.

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Correspondence to Rik R. Tykwinski.

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The authors declare no competing financial interests.

Supplementary information

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Supplementary information (PDF 3724 kb)

Supplementary information

Crystallographic data for compound 1b (CIF 29 kb)

Supplementary information

Crystallographic data for compound 4f (CIF 33 kb)

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Chalifoux, W., Tykwinski, R. Synthesis of polyynes to model the sp-carbon allotrope carbyne. Nature Chem 2, 967–971 (2010). https://doi.org/10.1038/nchem.828

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