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Protecting group and switchable pore-discriminating adsorption properties of a hydrophilic–hydrophobic metal–organic framework

Nature Chemistry volume 3, pages 304–310 (2011)Cite this article

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Abstract

Formed by linking metals or metal clusters through organic linkers, metal–organic frameworks are a class of solids with structural and chemical properties that mark them out as candidates for many emerging gas storage, separation, catalysis and biomedical applications. Important features of these materials include their high porosity and their flexibility in response to chemical or physical stimuli. Here, a copper-based metal–organic framework has been prepared in which the starting linker (benzene-1,3,5-tricarboxylic acid) undergoes selective monoesterification during synthesis to produce a solid with two different channel systems, lined by hydrophilic and hydrophobic surfaces, respectively. The material reacts differently to gases or vapours of dissimilar chemistry, some stimulating subtle framework flexibility or showing kinetic adsorption effects. Adsorption can be switched between the two channels by judicious choice of the conditions. The monoesterified linker is recoverable in quantitative yield, demonstrating possible uses of metal–organic frameworks in molecular synthetic chemistry as ‘protecting groups’ to accomplish selective transformations that are difficult using standard chemistry techniques.

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Figure 1: STAM-1 as a protecting group for the monomethyl esterification of benzene-1,3,5-tricarboxylic acid (BTC).
Figure 2: Structure of STAM-1.
Figure 3: Characterization of STAM-1.
Figure 4: Gas adsorption measurements on STAM-1.

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Acknowledgements

The authors acknowledge funding from the Engineering and Physical Sciences Research Council and the Gas Enabled Medical Innovation (GEMI) fund. R.E.M. is a Royal Society Wolfson Merit Award holder. The authors also thank G. Maurin for calculating the framework charges for the molecular modelling studies.

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Authors and Affiliations

  1. EaStCHEM School of Chemistry, University of St Andrews, St Andrews, KY16 9ST, UK

    M. Infas H. Mohideen, Bo Xiao, Paul S. Wheatley, Alistair C. McKinlay, Yang Li, Alexandra M. Z. Slawin, David W. Aldous, John M. Griffin, Sharon E. Ashbrook & Russell E. Morris

  2. Institute for Materials and Processes, School of Engineering, The University of Edinburgh, Edinburgh, EH9 3JL, UK

    Naomi F. Cessford & Tina Düren

  3. Northern Carbon Research Laboratories, Sir Joseph Swan Institute and School of Chemical Engineering and Advanced Materials, Bedson Building, Newcastle University, Newcastle upon Tyne, NE1 7RU, UK

    Xuebo Zhao, Rachel Gill & K. Mark Thomas

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  1. M. Infas H. Mohideen
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Contributions

M.I.H.M. and R.E.M. conceived and designed the experiments, and M.I.H.M. synthesized the materials. B.X., P.S.W., X.Z., R.G. and K.M.T. completed the adsorption experiments. M.I.H.M., Y.L., A.M.Z.S, D.W.A. and P.S.W. analysed the diffraction experiments. N.F.C. and T.D. completed the molecular modelling, and J.M.G. and S.E.A. the solid-state NMR.

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Correspondence to Russell E. Morris.

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Crystallographic data for STAM-1 (CIF 10 kb)

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Mohideen, M., Xiao, B., Wheatley, P. et al. Protecting group and switchable pore-discriminating adsorption properties of a hydrophilic–hydrophobic metal–organic framework. Nature Chem 3, 304–310 (2011). https://doi.org/10.1038/nchem.1003

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