Chemistry and Structure of a Host–Guest Relationship: The Power of NMR and X-ray Diffraction in Tandem
- 29 November 2012
- journal article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 135 (1), 392-399
- https://doi.org/10.1021/ja3096762
Abstract
An amine/amide mixed covalent organic tetrahedral cage 1 (H12) was synthesized and characterized. The H12 cage contains 12 amide NH groups plus four tertiary amine N groups, the latter of which are positioned in a pseudo-tetrahedral array. Crystallographic findings indicate that the tetrahedral host can adopt either a pseudo-C3 symmetric “compressed tetrahedron” structure, or one in which there are two sets of three stacked pyridine units related by a pseudo-S4 axis. The latter conformation is ideal for encapsulating small pentameric clusters, either a water molecule or a fluoride ion surrounded by a tetrahedral array of water molecules, i.e., H2O·4H2O or F–·4H2O, as observed crystallographically. In solution, however, 19F NMR spectroscopy indicates that H12 encapsulates fluoride ion through direct amide hydrogen bonding. By collectively combining one-dimensional 1H, 13C, and 19F with two-dimensional 1H–1H COSY, 1H–13C HSQC, and 1H–19F HETCOR NMR techniques, the solution binding mode of fluoride can be ascertained as consisting of four sets of independent structural subunits with C3 symmetry. A complex deuterium exchange process for the fluoride complex can also be unraveled by multiple NMR techniques.This publication has 72 references indexed in Scilit:
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