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A nanoporous two-dimensional polymer by single-crystal-to-single-crystal photopolymerization

Nature Chemistry volume 6, pages 774–778 (2014)Cite this article

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Abstract

In contrast to the wide number and variety of available synthetic routes to conventional linear polymers, the synthesis of two-dimensional polymers and unambiguous proof of their structure remains a challenge. Two-dimensional polymers—single-layered polymers that form a tiling network in exactly two dimensions—have potential for use in nanoporous membranes and other applications. Here, we report the preparation of a fluorinated hydrocarbon two-dimensional polymer that can be exfoliated into single sheets, and its characterization by high-resolution single-crystal X-ray diffraction analysis. The procedure involves three steps: preorganization in a lamellar crystal of a rigid monomer bearing three photoreactive arms, photopolymerization of the crystalline monomers by [4 + 4] cycloaddition, and isolation of individual two-dimensional polymer sheets. This polymer is a molecularly thin (~1 nm) material that combines precisely defined monodisperse pores of ~9 Å with a high pore density of 3.3 × 1013 pores cm−2. Atomic-resolution single-crystal X-ray structures of the monomer, an intermediate dimer and the final crystalline two-dimensional polymer were obtained and prove the single-crystal-to-single-crystal nature and molecular precision of the two-dimensional photopolymerization.

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Figure 1: Molecular structure and preorganization in fantrip monomer crystals.
Figure 2: Overview of the single-crystal-to-single-crystal transformations of fantrip.
Figure 3: X-ray structures of the solvent-free polymer.
Figure 4: Scanning electron microscopy (SEM) micrograph and atomic force microscopy (AFM) image of exfoliated sheets.

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Acknowledgements

This work was supported by the US National Science Foundation (CHE-09567702 and IIA-1301726) and the Swiss National Science Foundation (PBEZP2-140092). The authors thank A.D. Schlüter and J. Sakamoto for inspiring discussions and B. Kumar for preliminary synthetic work.

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Authors and Affiliations

  1. Department of Chemistry, University of Nevada, Reno, 89557-0216, Nevada, USA

    Patrick Kissel, Daniel J. Murray, William J. Wulftange, Vincent J. Catalano & Benjamin T. King

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  1. Patrick Kissel
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Contributions

P.K. performed the synthesis, photopolymerization and crystallography. V.J.C. and P.K. performed the analysis and interpretation of the X-ray data. D.J.M. performed the exfoliation, and obtained the AFM and SEM images. W.J.W. assisted with the synthesis. B.T.K. designed the monomer and advised on the project.

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Correspondence to Benjamin T. King.

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Supplementary information

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Supplementary information (PDF 12016 kb)

Supplementary information

Crystallographic data for compound fantrip (CIF 9742 kb)

Supplementary information

Crystallographic data for compound fantrip dimer (CIF 7078 kb)

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Crystallographic data for compound poly(fantrip) (CIF 7205 kb)

Supplementary information

Crystallographic data for compound solvent-free poly(fantrip) (CIF 808 kb)

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Kissel, P., Murray, D., Wulftange, W. et al. A nanoporous two-dimensional polymer by single-crystal-to-single-crystal photopolymerization. Nature Chem 6, 774–778 (2014). https://doi.org/10.1038/nchem.2008

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