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Triazolinediones enable ultrafast and reversible click chemistry for the design of dynamic polymer systems

Nature Chemistry volume 6, pages 815–821 (2014)Cite this article

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An Erratum to this article was published on 22 September 2014

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Abstract

With its focus on synthetic reactions that are highly specific and reliable, ‘click’ chemistry has become a valuable tool for many scientific research areas and applications. Combining the modular, covalently bonded nature of click-chemistry linkages with an ability to reverse these linkages and reuse the constituent reactants in another click reaction, however, is a feature that is not found in most click reactions. Here we show that triazolinedione compounds can be used in click-chemistry applications. We present examples of simple and ultrafast macromolecular functionalization, polymer–polymer linking and polymer crosslinking under ambient conditions without the need for a catalyst. Moreover, when triazolinediones are combined with indole reaction partners, the reverse reaction can also be induced at elevated temperatures, and the triazolinedione reacted with a different reaction partner, reversibly or irreversibly dependent on its exact nature. We have used this ‘transclick’ reaction to introduce thermoreversible links into polyurethane and polymethacrylate materials, which allows dynamic polymer-network healing, reshaping and recycling.

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Figure 1: Summary of applied TAD chemistry for click and transclick reactions.
Figure 2: Model reactions and synthesis of indole components.
Figure 3: Transclick study and theoretical rationalization of TAD reactions.
Figure 4: Irreversible polymer conjugation.
Figure 5: Reversible polymer conjugation.
Figure 6: Dynamic properties of TAD-based materials.

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Change history

  • 11 August 2014

    Technical issues with our online publication processes resulted in this Article being published the day after that referred to in the print version. The official date of publication is 11 August 2014.

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Acknowledgements

B. De Meyer is acknowledged for the measurements of the LC-SEC samples. S.B. and F.D. thank the Agency for Innovation by Science and Technology in Flanders for PhD scholarships. K.D.B. thanks the Research Foundation-Flanders (FWO) for the funding of his fellowship. H.G., F.D.P. and V.V.S. acknowledge the FWO (Vlaanderen), the Research Board of Ghent University and the Belgian Science Policy Office Interuniversity Attraction Poles (IAP) programme in the frame of IAP 7/05 for financial support. Computational resources and services used in this work were provided by Ghent University (Stevin Supercomputer Infrastructure).

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Authors and Affiliations

  1. Department of Organic Chemistry, Polymer Chemistry Research Group and Laboratory for Organic Synthesis, Ghent University, Krijgslaan 281 S4-bis, Ghent, B-9000, Belgium

    Stijn Billiet, Kevin De Bruycker, Frank Driessen, Johan M. Winne & Filip E. Du Prez

  2. Center for Molecular Modeling, Ghent University, Technologiepark 903, Zwijnaarde, B-9052, Belgium

    Hannelore Goossens & Veronique Van Speybroeck

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  1. Stijn Billiet
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Contributions

S.B, K.D.B., F.D. and H.G. performed the experiments. S.B., K.D.B., J.M.W. and F.D.P. conceived and designed the experiments. H.G. and V.V.S. were responsible for the theoretical calculations. S.B., J.M.W. and F.D.P wrote the paper. K.D.B prepared all the figures. All the authors discussed the results and commented on the manuscript at all stages.

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Correspondence to Johan M. Winne or Filip E. Du Prez.

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Billiet, S., De Bruycker, K., Driessen, F. et al. Triazolinediones enable ultrafast and reversible click chemistry for the design of dynamic polymer systems. Nature Chem 6, 815–821 (2014). https://doi.org/10.1038/nchem.2023

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