Article | Published:

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

Nature Chemistry volume 6, pages 774778 (2014) | Download Citation

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.

  • Compound C44H14F12

    Fantrip

  • Compound C47H23F12N3

    Tris(11-methyl-1,2,3,4-tetrafluoro-9,10-dihydroanthracen-9,10-imine)

  • Compound C9H5F4N

    2-Methyl-4,5,6,7-tetrafluoroisoindole

  • Compound C20H8Br6

    Hexabomotriptycene

  • Compound C20H14

    Triptycene

  • Compound C11H7F4N

    9-Methyl-5,6,7,8-tetrafluoro-1,4-dihydronaphthalen-l,4-imine

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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.

Author information

Affiliations

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

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

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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.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to Benjamin T. King.

Supplementary information

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    Supplementary information

    Supplementary information

Crystallographic information files

  1. 1.

    Supplementary information

    Crystallographic data for compound fantrip

  2. 2.

    Supplementary information

    Crystallographic data for compound fantrip dimer

  3. 3.

    Supplementary information

    Crystallographic data for compound poly(fantrip)

  4. 4.

    Supplementary information

    Crystallographic data for compound solvent-free poly(fantrip)

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DOI

https://doi.org/10.1038/nchem.2008

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