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A two-dimensional polymer prepared by organic synthesis

Abstract

Synthetic polymers are widely used materials, as attested by a production of more than 200 millions of tons per year, and are typically composed of linear repeat units. They may also be branched or irregularly crosslinked. Here, we introduce a two-dimensional polymer with internal periodicity composed of areal repeat units. This is an extension of Staudinger's polymerization concept (to form macromolecules by covalently linking repeat units together), but in two dimensions. A well-known example of such a two-dimensional polymer is graphene, but its thermolytic synthesis precludes molecular design on demand. Here, we have rationally synthesized an ordered, non-equilibrium two-dimensional polymer far beyond molecular dimensions. The procedure includes the crystallization of a specifically designed photoreactive monomer into a layered structure, a photo-polymerization step within the crystal and a solvent-induced delamination step that isolates individual two-dimensional polymers as free-standing, monolayered molecular sheets.

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Figure 1: Two-dimensional pre-organization in the monomer crystal.
Figure 2: SEM micrographs of photo-irradiated monomer crystals swollen in organic solvent.
Figure 3: AFM images of exfoliated sheets.
Figure 4: TEM and electron diffraction analysis of irradiated monomer crystals.

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Acknowledgements

The authors thank G. Wegner (MPI-P, Mainz) for useful advice, A. Renn (ETHZ), V. Sandoghdar (MPI-PL, Erlangen) and A. Grotzky (ETHZ) for help with solid-state UV/vis and fluorescence spectroscopy, J. Rabl (ETHZ), M. Solar (ETHZ), T. Weber (ETHZ) and T. Tomizaki (PSI, Villigen) for help with the X-ray crystallographic analyses, A. Eyssler (EMPA) and M. B. Willeke (ETHZ) for help with Raman measurements, M. Kory (ETHZ) and R. Hafner (ETHZ) for help with the model compound synthesis, and K. Feldman (ETHZ) and P. Smith (ETHZ) for providing access to their optical microscopy. This work was supported by ETH Zurich (TH-05 07-1 and ETH-26 10-2) and the Swiss National Science Foundation (200021-129660).

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Contributions

P.K. performed most of the experiments. R.E. conducted the TEM imaging and electron diffraction analysis. W.B.S. carried out the X-ray crystallographic analysis. M.D.R. assisted with interpretation of the electron diffraction pattern. B.T.K. simulated the polymer crystal structure. T.B. recorded the SEM images. S.G. assisted with setting up the in situ fluorescence spectroscopy. A.D.S. initiated the activities for two-dimensional polymer synthesis and coordinated the research. J.S. developed the concept and designed the monomer. J.S. and A.D.S. wrote the manuscript with input from all authors.

Corresponding author

Correspondence to Junji Sakamoto.

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The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary information (PDF 9158 kb)

Supplementary information

Crystallographic data for compound A. (CIF 25 kb)

Supplementary information

Crystallographic data for compound B. (CIF 64 kb)

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Kissel, P., Erni, R., Schweizer, W. et al. A two-dimensional polymer prepared by organic synthesis. Nature Chem 4, 287–291 (2012). https://doi.org/10.1038/nchem.1265

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