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In situ X-ray snapshot analysis of transient molecular adsorption in a crystalline channel

Nature Chemistry volume 6, pages 913–918 (2014)Cite this article

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Abstract

Molecular adsorption is a fundamental phenomenon in porous materials and is usually characterized by the efficiency and selectivity of molecular separations and reactions. However, for functional porous materials, analysis of the dynamic behaviour of molecular adsorbents is a major challenge. Here, we use in situ single-crystal X-ray diffraction to analyse multi-step molecular adsorption in a crystalline nanochannel of a metal-macrocycle framework. The pore surface of the metal-macrocycle framework crystal contains five different enantiomerically paired binding pockets, to which the adsorption of a (1R)-1-(3-chlorophenyl)ethanol solution was monitored with time. The resulting X-ray snapshot analyses suggest that the guest adsorption process takes a two-step pathway before equilibrium, in which the guest molecule is temporarily trapped by a neighbouring binding site. This demonstrates the potential for using X-ray analyses to visualize a transient state during a non-covalent self-assembly process.

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Figure 1: Schematic illustration of in situ X-ray observation of molecular adsorption within a liquid-filled porous crystal.
Figure 2: Synthesis and unit pore structure of a single-crystalline nanochannel of an MMF.
Figure 3: Experimental sequence for in situ X-ray snapshot analyses.
Figure 4: In situ X-ray crystallographic study of MMF containing (1R)-1-(3-chlorophenyl)ethanol.
Figure 5: Side view of MMF pores showing three observed guest binding modes in the (P)-Syn-tail and (P)-ellipsoidal pockets in the third XRD measurement.

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Acknowledgements

This research was supported in part by KAKENHI (nos. 21225003 and 23655117), the Japan Society for the Promotion of Science and MEXT, Japan. The authors acknowledge Takasago International Corporation for the provision of (1R)-1-(3-chlorophenyl)ethanol. The authors thank J. Tucker and J-L. Duprey for helpful discussions.

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Authors and Affiliations

  1. Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan

    Ryou Kubota, Shohei Tashiro & Mitsuhiko Shionoya

  2. Rigaku Co. Ltd, 3-9-2 Matsubaracho, Akishima, Tokyo, 196-8666, Japan

    Motoo Shiro

Authors
  1. Ryou Kubota
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  2. Shohei Tashiro
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Contributions

M. Shionoya and S.T. designed the project and analysed the results. All authors prepared the manuscript. R.K. performed the experimental work. M. Shiro confirmed the validity of the X-ray crystallographic analysis.

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Correspondence to Mitsuhiko Shionoya.

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The authors declare no competing financial interests.

Supplementary information

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Supplementary information (PDF 2175 kb)

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Crystallographic data for compound MMF_time1 (CIF 5595 kb)

Supplementary information

Crystallographic data for compound MMF_time2 (CIF 8022 kb)

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Crystallographic data for compound MMF_time3 (CIF 8013 kb)

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Crystallographic data for compound MMF_time4 (CIF 7958 kb)

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Kubota, R., Tashiro, S., Shiro, M. et al. In situ X-ray snapshot analysis of transient molecular adsorption in a crystalline channel. Nature Chem 6, 913–918 (2014). https://doi.org/10.1038/nchem.2044

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