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Issue 4, 2016
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[C–H⋯anion] interactions mediate the templation and anion binding properties of topologically non-trivial metal–organic structures in aqueous solutions

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Abstract

Two synthetic approaches—temperature variation and anion templation—allowed for the selective formation of a [2]catenane ([2]C4+) or a trefoil knot (TK6+), or for the enhanced formation of a Solomon link (SL8+), all from a simple set of starting materials (Zn(II) acetate, diformylpyridine (DFP) and a diamino-2,2′-bipyridine (DAB)) in mixed aqueous solutions. The catenane formed exclusively at 90 °C in a 1 : 1 mixed solvent of D2O and MeOD. In the presence of bromide ion as template, TK6+ formed exclusively at 50 °C in the same solvent. In the solid state, TK6+ hosts two bromide ions in its central cavity by forming six Csp2–H hydrogen bonds. In D2O, TK6+, which was originally prepared as a trifluoroacetate (TFA) salt, was found to exchange two TFA counterions for two monovalent anions of different sizes and shapes, which lodged within the knot's central cavity. In contrast to bromide, the larger triflate anion (CF3SO3) promoted the formation of SL8+, which was characterized by 1H NMR spectroscopy and mass spectrometry. Two dimensional heteronuclear 19F-1H-HOSEY NMR experiments detected CH⋯F interactions inside the cavity of SL8+. Thus, the product distribution of this dynamic link forming system is sensitive to temperature and the size and shape of the anion template, and one of the products, TK6+, is capable of binding a variety of monovalent anions in D2O with high affinity (with log β2 values of 4 to 6 being typical).

Graphical abstract: [C–H⋯anion] interactions mediate the templation and anion binding properties of topologically non-trivial metal–organic structures in aqueous solutions

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Supplementary files

Article information


Submitted
08 Nov 2015
Accepted
09 Feb 2016
First published
12 Feb 2016

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2016,7, 2524-2531
Article type
Edge Article

[C–H⋯anion] interactions mediate the templation and anion binding properties of topologically non-trivial metal–organic structures in aqueous solutions

R. A. Bilbeisi, T. Prakasam, M. Lusi, R. El Khoury, C. Platas-Iglesias, L. J. Charbonnière, J. Olsen, M. Elhabiri and A. Trabolsi, Chem. Sci., 2016, 7, 2524
DOI: 10.1039/C5SC04246A

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