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Gram-scale synthesis of two-dimensional polymer crystals and their structure analysis by X-ray diffraction

Nature Chemistry volume 6, pages 779784 (2014) | Download Citation

Abstract

The rise of graphene, a natural two-dimensional polymer (2DP) with topologically planar repeat units, has challenged synthetic chemistry, and has highlighted that accessing equivalent covalently bonded sheet-like macromolecules has, until recently, not been achieved. Here we show that non-centrosymmetric, enantiomorphic single crystals of a simple-to-make monomer can be photochemically converted into chiral 2DP crystals and cleanly reversed back to the monomer. X-ray diffraction established unequivocal structural proof for this synthetic 2DP, which has an all-carbon scaffold and can be synthesized on the gram scale. The monomer crystals are highly robust, can be easily grown to sizes greater than 1 mm and the resulting 2DP crystals exfoliated into nanometre-thin sheets. This unique combination of features suggests that these 2DPs could find use in membranes and nonlinear optics.

  • Compound C48H24N6O6

    1,5,10-(1,8)Trianthracena-2,4,5,8,9,11-hexaoxa 3,7-(1,3,5) ditriazinabicyclo [3.3.3]undecaphane

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Acknowledgements

T. Schweizer is thanked for building the ultraviolet reactor and the PID (proportional integral derivative)-controlled heating plate. We thank R. Verel for help with the acquisition of solid-state NMR spectra and G. Wegner, B. King, B. Batlogg, J. Leuthold and W. Steurer for helpful discussions. We further thank F. Heiligtag for the help with the acquisition of solid-state ultraviolet absorbance and fluorescence spectra and A. Reiser for assisting with AFM image acquisition and processing. P. Smith and K. Feldmann are thanked for the access to optical microscopy.

Author information

Affiliations

  1. Laboratory of Polymer Chemistry, Department of Materials, ETH Zürich, Vladimir-Prelog-Weg 5, 8093 Zürich, Switzerland

    • Max J. Kory
    • , Payam Payamyar
    • , Stan W. van de Poll
    •  & A. Dieter Schlüter
  2. Laboratory of Inorganic Chemistry, Small Molecule Crystallography Center, Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 1, 8093 Zürich, Switzerland

    • Michael Wörle
    •  & Nils Trapp
  3. Laboratory of Crystallography, Department of Materials, ETH Zürich, Vladimir-Prelog-Weg 5, 8093 Zürich, Switzerland

    • Thomas Weber
    •  & Julia Dshemuchadse

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Contributions

M.J.K. designed and performed most of the experiments. T.W., M.W. and N.T. carried out the X-ray crystal structure measurements, and analysed and interpreted the data. P.P. performed the AFM height analyses and helped with the acquisition of SEM images. S.W.v.d.P. carried out some of the exfoliation experiments under the supervision of M.J.K. J.D. performed the X-ray powder diffraction measurements and created the X-ray structure illustrations presented in this paper. A.D.S. initiated the activities for 2DP synthesis, designed the monomer and coordinated the research. A.D.S and M.J.K. wrote the paper.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to A. Dieter Schlüter.

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Crystallographic information files

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    Crystallographic data for compound 1

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    Crystallographic data for compound 1-partially polymerized

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    Crystallographic data for compound 1-polymer

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    Crystallographic data for compound 1-polymer-annealed

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DOI

https://doi.org/10.1038/nchem.2007

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