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Issue 11, 2014
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A solvent-resistant halogen bond

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Abstract

The effect of solvent on the stabilities of complexes involving a single H-bond or halogen-bond (X-bond) has been quantified. Association constants for binary complexes of 4-(phenylazo)phenol, molecular iodine, tetramethylurea and tetramethylthiourea have been measured in fifteen different solvents by UV/vis absorption and 1H NMR titration experiments. The stabilities of the H-bonded complexes decrease by more than three orders of magnitude with increasing solvent polarity. In contrast, the X-bonded complex of molecular iodine with tetramethylthiourea is remarkably insensitive to the nature of the solvent (association constants measured in alkanes and alcohols are similar). The results suggest that, in contrast to H-bonds, where electrostatics determine thermodynamic stability, charge-transfer interactions make a major contribution to the stability of these X-bonded complexes rendering them resistant to increases in solvent polarity.

Graphical abstract: A solvent-resistant halogen bond

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Publication details

The article was received on 12 Jun 2014, accepted on 09 Jul 2014 and first published on 30 Jul 2014


Article type: Edge Article
DOI: 10.1039/C4SC01746C
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Citation: Chem. Sci., 2014,5, 4179-4183
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    A solvent-resistant halogen bond

    C. C. Robertson, R. N. Perutz, L. Brammer and C. A. Hunter, Chem. Sci., 2014, 5, 4179
    DOI: 10.1039/C4SC01746C

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