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Triggered Exchange of Anionic for Neutral Guests inside a Cationic Coordination Cage

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    Communication

    Triggered Exchange of Anionic for Neutral Guests inside a Cationic Coordination Cage
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    † Institute of Inorganic Chemistry, Georg-August-University Göttingen, Tammannstraße 4, 37077 Göttingen, Germany
    ‡ Institute of Inorganic and Applied Chemistry, Univ. of Hamburg, Martin-Luther-King-Platz 6, 20146 Hamburg, Germany
    *[email protected]
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2015, 137, 3, 1060–1063
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    https://doi.org/10.1021/ja5130379
    Published January 8, 2015
    Copyright © 2015 American Chemical Society
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    Abstract

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    Molecular encapsulation processes under the control of an external trigger play a major role in biological signal transduction processes and enzyme catalysis. Here, we present an artificial mimic of a controllable host system that forms via self-assembly from a simple bis-monodentate ligand and Pd(II) cations. The resulting interpenetrated double cage features three consecutive pockets which initially contain one tetrafluoroborate anion, each. Activation of this host system with two halide anions triggers a conformational change that renders the central pocket susceptible to the uptake of small neutral guest molecules. Thereby, the pentacationic cage expels the central anion and replaces it with a neutral molecule to give a hexacationic species. The cage structures prior and after the halide triggered binding of benzene were examined by X-ray crystallography, ESI MS, and NMR techniques. The kinetics and thermodynamics of the encapsulation of benzene, cyclohexane, and norbornadiene are compared.

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    Synthetic procedures, further NMR, MS, and X-ray data. This material is available free of charge via the Internet at http://pubs.acs.org.

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    This article is cited by 163 publications.

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    Cite this: J. Am. Chem. Soc. 2015, 137, 3, 1060–1063
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