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Halogen-bonding-triggered supramolecular gel formation

Nature Chemistry volume 5, pages 42–47 (2013)Cite this article

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Abstract

Supramolecular gels are topical soft materials involving the reversible formation of fibrous aggregates using non-covalent interactions. There is significant interest in controlling the properties of such materials by the formation of multicomponent systems, which exhibit non-additive properties emerging from interaction of the components. The use of hydrogen bonding to assemble supramolecular gels in organic solvents is well established. In contrast, the use of halogen bonding to trigger supramolecular gel formation in a two-component gel (‘co-gel’) is essentially unexplored, and forms the basis for this study. Here, we show that halogen bonding between a pyridyl substituent in a bis(pyridyl urea) and 1,4-diiodotetrafluorobenzene brings about gelation, even in polar media such as aqueous methanol and aqueous dimethylsulfoxide. This demonstrates that halogen bonding is sufficiently strong to interfere with competing gel-inhibitory interactions and create a ‘tipping point’ in gel assembly. Using this concept, we have prepared a halogen bond donor bis(urea) gelator that forms co-gels with halogen bond acceptors.

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Figure 1: Manipulation of gel formation and destruction through competitive intermolecular interactions.
Figure 2: Chemical formulae of the compounds used to obtain supramolecular LMWGs.
Figure 3: Gel formation by halogen bonding.
Figure 4: Halogen bonding and water inclusion in the hydrate gel 2·3·2H2O.
Figure 5: Halogen bonding gel formation by two-component mixtures based on compound 4.
Figure 6: Co-gel formation between halogen bond acceptor and halogen bond donor bis(urea)s 1 and 4.

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Acknowledgements

J.W.S., K.F. and J.A.F. acknowledge funding from the Engineering and Physical Sciences Research Council and GlaxoSmithKline. P.M. and G.R. thank Fondazione Cariplo (project nos 2009-2550 and 2010-1351) for financial support.

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Authors and Affiliations

  1. NFMLab-DCMIC ‘Giulio Natta’, Politecnico di Milano, Via L. Mancinelli 7 IT-20131, Italy

    Lorenzo Meazza, Pierangelo Metrangolo & Giuseppe Resnati

  2. CNST-IIT@POLIMI, Via G. Pascoli 70/3, Milano, IT-20133, Italy

    Lorenzo Meazza, Pierangelo Metrangolo & Giuseppe Resnati

  3. Department of Chemistry, Durham University, South Road, Durham, DH1 3LE, UK

    Jonathan A. Foster, Katharina Fucke & Jonathan W. Steed

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  1. Lorenzo Meazza
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  4. Pierangelo Metrangolo
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Contributions

L.M. and J.A.F. undertook the synthesis of gelators, experimental studies and rheology measurements. K.F. carried out crystallographic measurements and PACHA calculations. P.M., G.R. and J.W.S. were responsible for the overall project concept, direction and coordination. All authors contributed to writing the manuscript.

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Correspondence to Pierangelo Metrangolo, Giuseppe Resnati or Jonathan W. Steed.

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Supplementary information

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Crystallographic data for the co-crystal 1-3 (CIF 20 kb)

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Crystallographic data for the co-crystal 2-3 (CIF 14 kb)

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Meazza, L., Foster, J., Fucke, K. et al. Halogen-bonding-triggered supramolecular gel formation. Nature Chem 5, 42–47 (2013). https://doi.org/10.1038/nchem.1496

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