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Hydrogen bonding vs. halogen bonding: the solvent decides

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  • Craig C. Robertson
  • James S. Wright
  • Elliot J. Carrington
  • Robin N. Perutz
  • Christopher A. Hunter
  • Lee Brammer


Publication details

JournalChemical Science
DateAccepted/In press - 17 May 2017
DateE-pub ahead of print - 1 Jun 2017
DatePublished (current) - 1 Aug 2017
Issue number8
Number of pages7
Pages (from-to)5392-5398
Early online date1/06/17
Original languageEnglish


Control of intermolecular interactions is integral to harnessing self-assembly in nature. Here we demonstrate that control of the competition between hydrogen bonds and halogen bonds, the two most highly studied directional intermolecular interactions, can be exerted by choice of solvent (polarity) to direct the self-assembly of co-crystals. Competitive co-crystal formation has been investigated for three pairs of hydrogen bond and halogen bond donors, which can compete for a common acceptor group. These competitions have been examined in seven different solvents. Product formation has been determined and phase purity has been examined by analysis of powder X-ray diffraction patterns. Formation of hydrogen-bonded co-crystals is favoured from less polar solvents and halogen-bonded co-crystals from more polar solvents. The solvent polarity at which the crystal formation switches from hydrogen-bond to halogen-bond dominance depends on the relative strengths of the interactions, but is not a function of the solution-phase interactions alone. The results clearly establish that an appreciation of solvent effects is critical to obtain control of the intermolecular interactions.

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© The Royal Society of Chemistry 2017. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details.

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