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Self-assembly of a layered two-dimensional molecularly woven fabric

Nature volume 588, pages 429–435 (2020)Cite this article

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Abstract

Fabrics—materials consisting of layers of woven fibres—are some of the most important materials in everyday life1. Previous nanoscale weaves2,3,4,5,6,7,8,9,10,11,12,13,14,15,16 include isotropic crystalline covalent organic frameworks12,13,14 that feature rigid helical strands interlaced in all three dimensions, rather than the two-dimensional17,18 layers of flexible woven strands that give conventional textiles their characteristic flexibility, thinness, anisotropic strength and porosity. A supramolecular two-dimensional kagome weave15 and a single-layer, surface-supported, interwoven two-dimensional polymer16 have also been reported. The direct, bottom-up assembly of molecular building blocks into linear organic polymer chains woven in two dimensions has been proposed on a number of occasions19,20,21,22,23, but has not previously been achieved. Here we demonstrate that by using an anion and metal ion template, woven molecular ‘tiles’ can be tessellated into a material consisting of alternating aliphatic and aromatic segmented polymer strands, interwoven within discrete layers. Connections between slowly precipitating pre-woven grids, followed by the removal of the ion template, result in a wholly organic molecular material that forms as stacks and clusters of thin sheets—each sheet up to hundreds of micrometres long and wide but only about four nanometres thick—in which warp and weft single-chain polymer strands remain associated through periodic mechanical entanglements within each sheet. Atomic force microscopy and scanning electron microscopy show clusters and, occasionally, isolated individual sheets that, following demetallation, have slid apart from others with which they were stacked during the tessellation and polymerization process. The layered two-dimensional molecularly woven material has long-range order, is birefringent, is twice as stiff as the constituent linear polymer, and delaminates and tears along well-defined lines in the manner of a macroscopic textile. When incorporated into a polymer-supported membrane, it acts as a net, slowing the passage of large ions while letting smaller ions through.

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Fig. 1: X-ray crystal structure of interwoven 3 × 3 molecular grid [Fe916](BF4)18, and the synthesis of thiol- and disulfide-derivatives 2, 3 and [Fe926](BF4)18.
Fig. 2: Bottom-up self-assembly of layered 2D molecularly woven fabric 4.
Fig. 3: Images of layered 2D molecularly woven fabric 4, and evidence for long-range order.
Fig. 4: Microscopy imaging of layered 2D molecularly woven fabric 4.
Fig. 5: Ion permeability studies on PVDF-supported membranes formed from unwoven linear polymer 3 and 2D woven polymer 4.

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Data availability

The data that support the findings of this study are available within the paper and its Supplementary Information, or are available from the Mendeley data repository (https://data.mendeley.com/) with the identifier https://doi.org/10.17632/zkt5km82r2.2.

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Acknowledgements

We thank the Engineering and Physical Sciences Research Council (EPSRC; EP/P027067/1), the European Research Council (ERC; Advanced Grant no. 786630), and the Defense Advanced Research Projects Agency (DARPA; Co-operative Agreement W911NF-17-2-0148) for funding; with networking contributions from the COST Action CA17139, EUTOPIA. The views, opinions and/or findings expressed are those of the authors and should not be interpreted as representing the official views or policies of the Department of Defense or the US Government. We also thank the Diamond Light Source (UK) for synchrotron beam time on I19 (XR029), the University of Manchester, Department of Chemistry microanalysis and mass spectrometry services, the Henry Royce Institute for Advanced Materials (funded through EPSRC grants EP/R00661X/1 and EP/P025021/1) for the use of facilities, S. Jantzen/Biocinematics for the video animations, and S. J. Rowan (University of Chicago) and R. P. Sijbesma (Eindhoven University) for comments that improved the draft manuscript. D.A.L. is a Royal Society Research Professor.

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Authors and Affiliations

  1. Department of Chemistry, University of Manchester, Manchester, UK

    David P. August, Robert A. W. Dryfe, Paige R. C. Kent, David A. Leigh, Jean-François Lemonnier, Christopher A. Muryn, Leoni I. Palmer, Yiwei Song & George F. S. Whitehead

  2. Henry Royce Institute, University of Manchester, Manchester, UK

    Robert A. W. Dryfe

  3. Department of Materials, National Graphene Institute, University of Manchester, Manchester, UK

    Sarah J. Haigh, Zheling Li & Robert J. Young

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Contributions

D.P.A., L.I.P., J.-F.L. and Y.S. carried out the synthesis and general characterization studies. G.F.S.W. solved the crystal structure of [Fe916](BF4)18. Z.L., C.A.M. and R.J.Y. carried out the AFM studies. Z.L. and R.J.Y. performed the Young’s modulus, polarized optical microscope and deformation experiments. S.J.H. conducted the transmission electron microscopy studies, and R.A.W.D. and P.R.C.K. conducted the ion permeation studies. D.A.L. directed the research. All authors contributed to the analysis of the results and the writing of the manuscript. Authors are listed alphabetically in view of the broad range of experimental techniques used in this study.

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Correspondence to David A. Leigh.

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Peer review information Nature thanks the anonymous reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Experimental procedures, methods and characterisation data.

Video 1

(MPEG-4) Animation of the assembly of the 2D molecularly woven fabric. Video credit: Stuart Jantzen (Biocinematics).

Video 2

Supplementary Video 2 (MPEG-4) - Animation of AFM of a layered sheet of the 2D molecularly woven fabric. Video credit: Stuart Jantzen (Biocinematics).

Video 3

Supplementary Video 3 (MPEG-4) - Animation of the fracturing and delamination process of a layered sheet of the 2D molecularly woven fabric on a polyester support under strain. Video credit: Stuart Jantzen (Biocinematics).

Video 4

Supplementary Video 4 (MPEG-4) - Animation of Young’s modulus determination by AFM on the 2D molecularly woven fabric and the corresponding unwoven linear polymer. Video credit: Stuart Jantzen (Biocinematics).

Video 5

Supplementary Video 5 (MPEG-4) - Animation of the ion permeability studies on PVDF-supported membranes formed from (i) the 2D molecularly woven fabric and (ii) the corresponding unwoven linear polymer. Video credit: Stuart Jantzen (Biocinematics).

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August, D.P., Dryfe, R.A.W., Haigh, S.J. et al. Self-assembly of a layered two-dimensional molecularly woven fabric. Nature 588, 429–435 (2020). https://doi.org/10.1038/s41586-020-3019-9

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