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Crystalline molecular flasks

Nature Chemistry volume 3, pages 349–358 (2011)Cite this article

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Abstract

A variety of host compounds have been used as molecular-scale reaction vessels, protecting guests from their environment or restricting the space available around them, thus favouring particular reactions. Such molecular 'flasks' can endow guest molecules with reactivities that differ from those in bulk solvents. Here, we extend this concept to crystalline molecular flasks, solid-state crystalline networks with pores within which pseudo-solution-state reactions can take place. As the guest molecules can spontaneously align along the walls and channels of the hosts, structural changes in the substrates can be directly observed by in situ X-ray crystallography during reaction. Recently, this has enabled observation of the molecular structures of transient intermediates and other labile species, in the form of sequential structural snapshots of the chemical transformation. Here, we describe the principles, development and applications of crystalline molecular flasks.

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Figure 1: Schematic representations of two types of crystalline-state reactions.
Figure 2: Self-assembled cage as a crystalline molecular flask.
Figure 3: SCSC reactions within calix[4]arene crystals.
Figure 4: Guest inclusion in porous network complexes.
Figure 5: Post-synthetic modifications of porous network complexes analysed by X-ray single crystallography.
Figure 6: Modular synthesis of a porous network complex.
Figure 7: A variety of SCSC transformations within a biporous network.
Figure 8: Single crystallographic determination of a hemiaminal intermediate.

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Authors and Affiliations

  1. Department of Applied Chemistry, School of Engineering, The University of Tokyo, Hongo, Bunkyo-ku, 113-8656, Tokyo, Japan

    Yasuhide Inokuma & Makoto Fujita

  2. Division of Advanced Materials Science (WCU project) Pohang University of Science and Technology (POSTECH), San 31 Hyojadong, 790-784, Pohang, South Korea

    Masaki Kawano

  3. Core Research for Evolutional Science and Technology (CREST), Japan Science and Technology Agency (JST), Hongo, Bunkyo-ku, 113-8656, Tokyo, Japan

    Makoto Fujita

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  1. Yasuhide Inokuma
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Correspondence to Makoto Fujita.

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Inokuma, Y., Kawano, M. & Fujita, M. Crystalline molecular flasks. Nature Chem 3, 349–358 (2011). https://doi.org/10.1038/nchem.1031

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