Tunable adhesion from stoichiometry-controlled and sequence-defined supramolecular polymers emerges hierarchically from cyanostar-stabilized anion–anion linkages


Journal article


Wei Zhao, Joshua Tropp, Bo Qiao, Maren Pink, Jason D Azoulay, Amar H Flood
Journal of the American Chemical Society, vol. 142(5), 2020, pp. 2579-2591


Cite

Cite

APA   Click to copy
Zhao, W., Tropp, J., Qiao, B., Pink, M., Azoulay, J. D., & Flood, A. H. (2020). Tunable adhesion from stoichiometry-controlled and sequence-defined supramolecular polymers emerges hierarchically from cyanostar-stabilized anion–anion linkages. Journal of the American Chemical Society, 142(5), 2579–2591. https://doi.org/10.1021/jacs.9b12645


Chicago/Turabian   Click to copy
Zhao, Wei, Joshua Tropp, Bo Qiao, Maren Pink, Jason D Azoulay, and Amar H Flood. “Tunable Adhesion from Stoichiometry-Controlled and Sequence-Defined Supramolecular Polymers Emerges Hierarchically from Cyanostar-Stabilized Anion–Anion Linkages.” Journal of the American Chemical Society 142, no. 5 (2020): 2579–2591.


MLA   Click to copy
Zhao, Wei, et al. “Tunable Adhesion from Stoichiometry-Controlled and Sequence-Defined Supramolecular Polymers Emerges Hierarchically from Cyanostar-Stabilized Anion–Anion Linkages.” Journal of the American Chemical Society, vol. 142, no. 5, 2020, pp. 2579–91, doi:10.1021/jacs.9b12645.


BibTeX   Click to copy

@article{wei2020a,
  title = {Tunable adhesion from stoichiometry-controlled and sequence-defined supramolecular polymers emerges hierarchically from cyanostar-stabilized anion–anion linkages},
  year = {2020},
  issue = {5},
  journal = {Journal of the American Chemical Society},
  pages = {2579-2591},
  volume = {142},
  doi = {10.1021/jacs.9b12645},
  author = {Zhao, Wei and Tropp, Joshua and Qiao, Bo and Pink, Maren and Azoulay, Jason D and Flood, Amar H}
}

Sequence-controlled supramolecular polymers offer new design paradigms for generating stimuli-responsive macromolecules with enhanced functionalities. The dynamic character of supramolecular links present challenges to sequence definition in extended supramolecular macromolecules, and design principles remain nascent. Here, we demonstrate the first example of using stoichiometry-control to specify the monomer sequence in a linear supramolecular polymer by synthesizing both a homopolymer and an alternating copolymer from the same glycol-substituted cyanostar macrocycle and phenylene-linked diphosphate monomers. A 2:1 stoichiometry between macrocycle and diphosphate produces a supramolecular homopolymer of general formula (A)n comprised of repeating units of cyanostar-stabilized phosphate–phosphate dimers. Using a 1:1 stoichiometry, an alternating (AB)n structure is produced with half the phosphate dimers now stabilized by the additional counter cations that emerge hierarchically after forming the stronger cyanostar-stabilized phosphate dimers. These new polymer materials and binding motifs are sufficient to bear normal and shear stress to promote significant and tunable adhesive properties. The homopolymer (A)n, consisting of cyanostar-stabilized anti-electrostatic linkages, shows adhesion strength comparable to commercial superglue formulations based on polycyanoacrylate but is thermally reversible. Unexpectedly, and despite including traditional ionic linkages, the alternating copolymer (AB)n shows weaker adhesion strength more similar to commercial white glue based on poly(vinyl acetate). Thus, the adhesion properties can be tuned over a wide range by simply controlling the stoichiometric ratio of monomers. This study offers new insight into supramolecular polymers composed of custom-designed anion and receptor monomers and demonstrates the utility of emerging functional materials based on anion–anion linkages.




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