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Synthesis of γ-graphyne using dynamic covalent chemistry

Nature Synthesis volume 1, pages 449–454 (2022)Cite this article

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An Author Correction to this article was published on 14 July 2022

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Abstract

Most attempts to synthesize graphynes are limited to using irreversible coupling reactions, which often result in the formation of nanometre-scale materials that lack long-range order. Here the periodically sp–sp2-hybridized carbon allotrope, γ-graphyne, was synthesized in bulk via a reversible dynamic alkyne metathesis of alkynyl-substituted benzene monomers. The balance between kinetic and thermodynamic control was managed through the simultaneous use of two different hexa-alkynyl-substituted benzenes as the comonomers to yield crystalline γ-graphyne. Additionally, the ABC staggered interlayer stacking of the graphyne was revealed using powder X-ray and electron diffraction. Finally, the folding behaviour of the few-layer graphyne was also observed on exfoliation, and showed step edges within a single graphyne flake with a height of 9 nm.

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Fig. 1: Synthesis of γ-graphyne.
Fig. 2: Structural characterization of γ-graphyne.
Fig. 3: Crystal structure of γ-graphyne with the unit cell and primitive cell.
Fig. 4: Folding behaviour of γ-graphyne.

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Data availability

Experimental data and characterization data are provided in the Supplementary Information. Crystallographic data for the structure HPB reported in this Article has been deposited at the Cambridge Crystallographic Data Centre (CCDC), under deposition number 2111647. Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/.

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Acknowledgements

We thank J. Choi (University of Colorado Boulder) for helpful discussions on the electrochemistry tests and B. Lama (University of Colorado Boulder) for solid-state NMR spectroscopy data acquisition. W.Z. acknowledges the National Science Foundation (DMR-1420736). Y.Z. acknowledges the National Natural Science Foundation of China (31202117). Y.H. thanks the Summer Graduate Fellowship support from University of Colorado Boulder. The authors gratefully acknowledge use of the Materials Research X-Ray Diffraction Facility at the University of Colorado Boulder (RRID: SCR_019304), with instrumentation supported by NSF MRSEC grant DMR-1420736.

Author information

Authors and Affiliations

  1. Department of Chemistry, University of Colorado Boulder, Boulder, CO, USA

    Yiming Hu, Yinghua Jin, Shaofeng Huang, Jingyi Wu, Lacey J. Wayment & Wei Zhang

  2. College of Polymer Science and Engineering, Qingdao University of Science and Technology, Qingdao, China

    Chenyu Wu, Qingyan Pan & Yingjie Zhao

  3. Department of Physics and JILA, University of Colorado, Boulder, CO, USA

    Rui Lyu & Markus B. Raschke

  4. Department of Physics and Liquid Crystal Materials Research Center, University of Colorado, Boulder, CO, USA

    Vikina Martinez & Noel A. Clark

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  1. Yiming Hu
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Contributions

Y.H., Y.Z. and W.Z. conceived the idea and led the project. Y.H., S.H., J.W. and L.J.W. conducted the synthesis. C.W. conducted the modelling. Q.P. and Y.Z. conducted the transmission electron microscopy. R.L. and M.B.R. conducted the AFM. V.M. and N.A.C. conducted the WAXS. Y.H., Y.J., Y.Z. and W.Z. interpreted the results and Y.H., Y.J. and W.Z. wrote the manuscript.

Corresponding authors

Correspondence to Yingjie Zhao or Wei Zhang.

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Competing interests

Y.H. and W.Z. are inventors on a US patent application submitted by University of Colorado Boulder. The other authors do not have any competing interests.

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Peer review information

Nature Synthesis thanks the anonymous reviewers for their contribution to the peer review of this work. Primary Handling editor: Peter Seavill, in collaboration with the Nature Synthesis team.

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Supplementary information

Supplementary Information

Experimental Details and Supplementary Figs. 1–28, discussion and Tables 1–4.

Supplementary Data 1

Crystallographic data of 1,2,3,4,5,6-hexapropynylbenzene (HPB), CCDC 2111647

Source data

Source Data Fig. 4c

The Excel sheet contains height plot data for the layered structure of exfoliated γ-graphyne.

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Hu, Y., Wu, C., Pan, Q. et al. Synthesis of γ-graphyne using dynamic covalent chemistry. Nat. Synth 1, 449–454 (2022). https://doi.org/10.1038/s44160-022-00068-7

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