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Thermally bisignate supramolecular polymerization

Nature Chemistry volume 9, pages 1133–1139 (2017)Cite this article

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Abstract

One of the enticing characteristics of supramolecular polymers is their thermodynamic reversibility, which is attractive, in particular, for stimuli-responsive applications. These polymers usually disassemble upon heating, but here we report a supramolecular polymerization that occurs upon heating as well as cooling. This behaviour arises from the use of a metalloporphyrin-based tailored monomer bearing eight amide-containing side chains, which assembles into a highly thermostable one-dimensional polymer through π-stacking and multivalent hydrogen-bonding interactions, and a scavenger, 1-hexanol, in a dodecane-based solvent. At around 50 °C, the scavenger locks the monomer into a non-polymerizable form through competing hydrogen bonding. On cooling, the scavenger preferentially self-aggregates, unlocking the monomer for polymerization. Heating also results in unlocking the monomer for polymerization, by disrupting the dipole and hydrogen-bonding interactions with the scavenger. Analogous to ‘upper and lower critical solution temperature phenomena’ for covalently bonded polymers, such a thermally bisignate feature may lead to supramolecular polymers with tailored complex thermoresponsive properties.

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Figure 1: Structure of the porphyrin monomers and representation of their assembly.
Figure 2: Schematic representation of thermally bisignate supramolecular polymerization.
Figure 3: Thermodynamic association/dissociation behaviours of 1-hexanol (C6H13OH) in dodecane*.
Figure 4: Thermally bisignate supramolecular polymerization of (S)PORCu and (R)PORCu in dodecane* containing C6H13OH.
Figure 5: Thermally bisignate supramolecular polymerization of (S)PORCu in dodecane* containing C6H13OH.
Figure 6: Tuning of the optical window by thermally bisignate supramolecular polymerization.

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Acknowledgements

This work was supported by the Japan Society for the Promotion of Science (JSPS) through its Grants-in-Aid for Specially Promoted Research (25000005) on ‘Physically Perturbed Assembly for Tailoring High-Performance Soft Materials with Controlled Macroscopic Structural Anisotropy’, Young Scientist A (15H05487), Coordination Asymmetry (JP17H05394) together (grants sponsored by the Japan Society for the Promotion of Science) with the ImPACT Program of the Council for Science, Technology and Innovation (Cabinet Office, Government of Japan). K.V.R. thanks the JSPS for a post-doctoral fellowship.

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  1. RIKEN Center for Emergent Matter Science, 2-1 Hirosawa, Wako, 351-0198, Saitama, Japan

    Kotagiri Venkata Rao, Daigo Miyajima, Atsuko Nihonyanagi & Takuzo Aida

  2. Department of Chemistry and Biotechnology, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, 113-8656, Tokyo, Japan

    Kotagiri Venkata Rao & Takuzo Aida

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Contributions

K.V.R. designed and performed all of the experiments. D.M. and T.A. co-designed the experiments. A.N. synthesized all of the porphyrin derivatives. K.V.R., D.M. and T.A. analysed the data and wrote the manuscript.

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Correspondence to Daigo Miyajima or Takuzo Aida.

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Venkata Rao, K., Miyajima, D., Nihonyanagi, A. et al. Thermally bisignate supramolecular polymerization. Nature Chem 9, 1133–1139 (2017). https://doi.org/10.1038/nchem.2812

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