Issue 2, 2017

pH controlled assembly of a self-complementary halogen-bonded dimer

Abstract

Phenols and their corresponding phenoxide anions can form halogen bonds with neutral iodotriazoles. The strength of these interactions depends critically on the protonation state of the oxygen atom – the interaction of the phenoxide anion is more than an order of magnitude stronger than the corresponding phenol. The assembly of a molecule bearing both an iodotriazole and a phenoxide anion into a self-complementary dimer, stabilised by two halogen bonds between the phenoxide anions and the neutral iodotriazoles has been demonstrated. The corresponding phenol shows no halogen bond mediated assembly either in the solid or in the solution state. This assembly process can be actuated simply by a change in protonation state – treatment of the phenol with one equivalent of base results in deprotonation and assembly of the dimer. The structure of the homodimer formed by the phenoxide-bearing iodotriazole has been determined in the solid state and 19F NMR spectroscopy demonstrates that the assembled dimer persists in solution and that it has significant stability. 19F NMR spectroscopy has also been used to demonstrate that the assembly process is completely reversible.

Graphical abstract: pH controlled assembly of a self-complementary halogen-bonded dimer

Supplementary files

Article information

Article type
Edge Article
Submitted
17 Aug 2016
Accepted
17 Sep 2016
First published
19 Sep 2016
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2017,8, 938-945

pH controlled assembly of a self-complementary halogen-bonded dimer

L. Maugeri, E. M. G. Jamieson, D. B. Cordes, A. M. Z. Slawin and D. Philp, Chem. Sci., 2017, 8, 938 DOI: 10.1039/C6SC03696A

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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