Article | Published:

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


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

Access optionsAccess options

Rent or Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.


  1. 1.

    Photodimerization in the solid state. Pure Appl. Chem. 12, 647–678 (1971).

  2. 2.

    Topochemical reactions of monomers with conjugated triple bonds. I. Polymerization of 2,4-hexadiyn-1,6-diol derivatives in crystalline state. Z. Naturforsch. 24B, 824–832 (1969).

  3. 3.

    et al. A two-dimensional polymer prepared by organic synthesis. Nature Chem. 4, 287–291 (2012).

  4. 4.

    et al. A two-dimensional polymer from the anthracene dimer and triptycene motifs. J. Am. Chem. Soc. 135, 14134–14140 (2013).

  5. 5.

    , , & Two-dimensional polymers: just a dream of synthetic chemists? Angew. Chem. Int. Ed. 48, 1030–1069 (2009).

  6. 6.

    & Rationally synthesized two-dimensional polymers. Nature Chem. 5, 453–465 (2013).

  7. 7.

    Concerning polymerization. Ber. Dtsch. Chem. Ges. 53, 1073–1085 (1920).

  8. 8.

    et al. Delamination of layered covalent organic frameworks. Small 7, 1207–1211 (2011).

  9. 9.

    et al. A 2D covalent organic framework with 4.7-nm pores and insight into its interlayer stacking. J. Am. Chem. Soc. 133, 19416–19421(2011).

  10. 10.

    et al. Single layers of a multifunctional laminar Cu(I,II) coordination polymer. Chem. Commun. 46, 3262–3264 (2010).

  11. 11.

    , & Top-down fabrication of crystalline metal–organic framework nanosheets. Chem. Commun. 47, 8436–8438 (2011).

  12. 12.

    et al. Solvent-induced delamination of a multifunctional two dimensional coordination polymer. Adv. Mater. 25, 2141–2146 (2013).

  13. 13.

    et al. Synthesis of free-standing, monolayered organometallic sheets at the air/water interface. Angew. Chem. Int. Ed. 50, 7879–7884 (2011).

  14. 14.

    et al. Square-micrometer-sized, free-standing organometallic sheets and their square-centimeter-sized multilayers on solid substrates. Macromol. Rapid Commun. 34, 1670–1680 (2013).

  15. 15.

    et al. Synthesis of a covalent monolayer sheet by photochemical anthracene dimerization at the air/water interface and its mechanical characterization by AFM indentation. Adv. Mater. 26, 2052–2058 (2014).

  16. 16.

    & Bulk synthesis of exfoliated two-dimensional polymers using hydrazone-linked covalent organic frameworks. J. Am. Chem. Soc. 135, 14952–14955 (2013).

  17. 17.

    et al. Oriented 2D covalent organic framework thin films on single-layer graphene. Science 332, 228–231 (2011).

  18. 18.

    et al. Stability and exfoliation of germanane: a germanium graphane analogue. ACS Nano 7, 4414–4421 (2013).

  19. 19.

    , , & A facile wet chemistry approach towards unilamellar tin sulfide nanosheets from Li4xSn1–xS2 solid solutions. J. Mater. Chem. A 2, 6100–6106 (2014).

  20. 20.

    , , & Graphene-like two dimensional materials. Chem. Rev. 113, 3766–3798 (2013).

  21. 21.

    , & Constructing monocrystalline covalent organic networks by polymerization. Nature Chem. 5, 830–834 (2013).

  22. 22.

    et al. Porous, crystalline, covalent organic frameworks. Science 310, 1166–1170 (2005).

  23. 23.

    et al. Crystalline covalent organic frameworks with hydrazone linkages. J. Am. Chem. Soc. 133, 11478–11481 (2011).

  24. 24.

    , & Porous, covalent triazine-based frameworks prepared by ionothermal synthesis. Angew. Chem. Int. Ed. 47, 3450–3453 (2008).

  25. 25.

    , , & Facile synthesis and theoretical conformation analysis of a triazine-based double-decker rotor molecule with three anthracene blades. Chem. Eur. J. 20, 6934–6938 (2014).

  26. 26.

    Organic reactions in the solid state: accident and design. Pure Appl. Chem. 51, 1965–1082 (1979).

  27. 27.

    et al. High-yield production of graphene by liquid-phase exfoliation of graphite. Nature Nanotech. 3, 563–568 (2008).

  28. 28.

    Molecular chirality in surface science. Surf. Sci. 613, 1–5 (2013).

  29. 29.

    , , & Photodimerization of anthracenes in fluid solutions: (part 2) mechanistic aspects of the photocycloaddition and of the photochemical and thermal cleavage. Chem. Soc. Rev. 30, 248–263 (2001).

  30. 30.

    et al. Reversible photodimerization: a new type of photochromism. Appl. Optics 11, 533–548 (1972).

Download references


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


  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


  1. Search for Max J. Kory in:

  2. Search for Michael Wörle in:

  3. Search for Thomas Weber in:

  4. Search for Payam Payamyar in:

  5. Search for Stan W. van de Poll in:

  6. Search for Julia Dshemuchadse in:

  7. Search for Nils Trapp in:

  8. Search for A. Dieter Schlüter in:


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.

Supplementary information

PDF files

  1. 1.

    Supplementary information

    Supplementary information

Crystallographic information files

  1. 1.

    Supplementary information

    Crystallographic data for compound 1

  2. 2.

    Supplementary information

    Crystallographic data for compound 1-partially polymerized

  3. 3.

    Supplementary information

    Crystallographic data for compound 1-polymer

  4. 4.

    Supplementary information

    Crystallographic data for compound 1-polymer-annealed

  5. 5.

    Supplementary information

    Crystallographic data for compound 1_depolymerized

About this article

Publication history





Further reading