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X-ray Crystallographic Studies on the Noncovalent Syntheses of Supermolecules

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Abstract

An approach to the supramolecular syntheses of discrete multicomponent aggregates of noncovalently bound molecules, i.e., supermolecules, is described. This approach involved the careful analysis of X-ray crystal structures so as to permit a gradual increase in superstructural complexity. Many elaborate supermolecules were synthesized noncovalently from dialkylammonium-containing cations and crown ethers, following the initial observation that the dibenzylammonium ion threads through dibenzo[24]crown-8 to generate a singly stranded, singly encircled [2]pseudorotaxane, principally as a result of \([{\text{N}}^{\text{ + }} - {\text{H}} \cdot \cdot \cdot {\text{O}}]\) and \([{\text{C}} - {\text{H}} \cdot \cdot \cdot {\text{O}}]\) hydrogen bond formation. The scope of the fundamental recognition motif obtained from this initial observation was then broadened, through the use of thread-like ions with multiple dialkylammonium centers and/or larger crown ethers, so that multiply stranded and/or multiply encircled pseudorotaxanes could be prepared. Cations bearing both dialkylammonium and crown ether recognition sites were also used for the nocovalent synthesis of a discrete daisy chain supermacrocycle and the basic recognition motif was combined with other motifs for the production of a wide range of novel superarchitectures. As a greater understanding of the noncovalent interactions governing the self-assembly of the complex superarchitectures was acquired, new protocols for the noncovalent syntheses of doubly docked pseudorotaxanes and interwoven supramolecular bundles, including a supramolecular analogue of the photosynthetic special pair, were developed. The discovery that anions can play a prominent role in the solid-state self-assembly of some of the supermolecules was a valuable spinoff of the research.

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Authors and Affiliations

  1. Department of Chemistry and Biochemistry, University of California, Los Angeles, California, 90095

    Matthew C. T. Fyfe & J. Fraser Stoddart

  2. Department of Chemistry, Imperial College, South Kensington, London, SW7 2AY

    David J. Williams

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Fyfe, M.C.T., Stoddart, J.F. & Williams, D.J. X-ray Crystallographic Studies on the Noncovalent Syntheses of Supermolecules. Structural Chemistry 10, 243–259 (1999). https://doi.org/10.1023/A:1021844715425

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