Journal
NATURE CHEMISTRY
Volume 6, Issue 9, Pages 774-778Publisher
NATURE PUBLISHING GROUP
DOI: 10.1038/nchem.2008
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Funding
- US National Science Foundation [CHE-09567702, IIA-1301726]
- Swiss National Science Foundation [PBEZP2-140092]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [0957702] Funding Source: National Science Foundation
- Swiss National Science Foundation (SNF) [PBEZP2_140092] Funding Source: Swiss National Science Foundation (SNF)
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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 (similar to 1 nm) material that combines precisely defined monodisperse pores of similar to 9 angstrom with a high pore density of 3.3 x 10(13) 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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