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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 779–784 (2014)Cite this article

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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.

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Figure 1: Rotor-shaped anthracene monomer 1 and the anthracene dimerization that enables 2DP growth.
Figure 2: Crystal structures of monomer and polymer crystals.
Figure 3: Products of swelling and exfoliation.
Figure 4: Reversibility of polymerization.

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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.

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Authors and Affiliations

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

    Max J. Kory, Payam Payamyar, Stan W. van de Poll & A. Dieter Schlüter

  2. Department of Chemistry and Applied Biosciences, Laboratory of Inorganic Chemistry, Small Molecule Crystallography Center, ETH Zürich, Vladimir-Prelog-Weg 1, Zürich, 8093, Switzerland

    Michael Wörle & Nils Trapp

  3. Department of Materials, Laboratory of Crystallography, ETH Zürich, Vladimir-Prelog-Weg 5, Zürich, 8093, Switzerland

    Thomas Weber & Julia Dshemuchadse

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  1. Max J. Kory
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  8. A. Dieter Schlüter
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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.

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Correspondence to A. Dieter Schlüter.

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The authors declare no competing financial interests.

Supplementary information

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Supplementary information (PDF 5858 kb)

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Crystallographic data for compound 1 (CIF 1670 kb)

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Crystallographic data for compound 1-partially polymerized (CIF 34 kb)

Supplementary information

Crystallographic data for compound 1-polymer (CIF 673 kb)

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Crystallographic data for compound 1-polymer-annealed (CIF 4147 kb)

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Crystallographic data for compound 1_depolymerized (CIF 34 kb)

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Kory, M., Wörle, M., Weber, T. et al. Gram-scale synthesis of two-dimensional polymer crystals and their structure analysis by X-ray diffraction. Nature Chem 6, 779–784 (2014). https://doi.org/10.1038/nchem.2007

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