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Control over differentiation of a metastable supramolecular assembly in one and two dimensions

Nature Chemistry volume 9, pages 493–499 (2017)Cite this article

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Abstract

Molecular self-assembly under kinetic control is expected to yield nanostructures that are inaccessible through the spontaneous thermodynamic process. Moreover, time-dependent evolution, which is reminiscent of biomolecular systems, may occur under such out-of-equilibrium conditions, allowing the synthesis of supramolecular assemblies with enhanced complexities. Here we report on the capacity of a metastable porphyrin supramolecular assembly to differentiate into nanofibre and nanosheet structures. Mechanistic studies of the relationship between the molecular design and pathway complexity in the self-assembly unveiled the energy landscape that governs the unique kinetic behaviour. Based on this understanding, we could control the differentiation phenomena and achieve both one- and two-dimensional living supramolecular polymerization using an identical monomer. Furthermore, we found that the obtained nanostructures are electronically distinct, which illustrates the pathway-dependent material properties.

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Figure 1: Molecular design.
Figure 2: Self-assembly energy landscapes of porphyrin derivatives.
Figure 3: Kinetic and thermodynamic studies of the self-assembly behaviour of 5 and 6.
Figure 4: Differentiation of a metastable supramolecular assembly.
Figure 5: Seeded control over differentiation of a metastable supramolecular assembly.

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Acknowledgements

This work was supported by KAKENHI (no. 15H05483), Scientific Research on Innovative Arias ‘π-System figuration: control of electron and structural dynamism for innovative functions (no. 26102009 and no. 26102011)’, ‘Dynamical ordering of biomolecular systems for creation of integrated functions (No. 16H00787)’ and the Nanotechnology Network Project from the Ministry of Education, Culture, Sports, Science and Technology, Japan. T.F. thanks the Japan Society for the Promotion of Science for a research fellowship for young scientist (16J02156). Financial support from the Sekisui Chemical Grant Program is also acknowledged.

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Authors and Affiliations

  1. National Institute for Materials Science (NIMS), 1-2-1 Sengen, Tsukuba, 305-0047, Ibaraki, Japan

    Tomoya Fukui, Yoshitaka Matsushita, Takeshi Yasuda, Masayuki Takeuchi & Kazunori Sugiyasu

  2. Department of Materials Science and Engineering, Graduate School of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, 305-8577, Ibaraki, Japan

    Tomoya Fukui & Masayuki Takeuchi

  3. Department of Chemistry, Faculty of Science, Shizuoka University, 836 Ohya, Suruga-ku, 422-8529, Shizuoka, Japan

    Shinnosuke Kawai

  4. Department of Bioengineering, Nagaoka University of Technology, 1603-1 Kamitomioka, Nagaoka, 940-2188, Niigata, Japan

    Satoko Fujinuma

  5. Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-ku, 615-8510, Kyoto, Japan

    Tsuneaki Sakurai & Shu Seki

Authors
  1. Tomoya Fukui
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Contributions

K.S. directed the project. T.F. carried out most of the experimental work except that mentioned below. S.K. contributed to the kinetic analysis of living supramolecular polymerization. S.F. synthesized some of the intermediates. Y.M. conducted powder X-ray diffraction measurement. T.Y. carried out PYS measurements. T.S. and S.S. performed FPTRMC measurements. T.F., M.T. and K.S. discussed the results and co-wrote the manuscript. All the authors commented on the manuscript.

Corresponding authors

Correspondence to Masayuki Takeuchi or Kazunori Sugiyasu.

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The authors declare no competing financial interests.

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Fukui, T., Kawai, S., Fujinuma, S. et al. Control over differentiation of a metastable supramolecular assembly in one and two dimensions. Nature Chem 9, 493–499 (2017). https://doi.org/10.1038/nchem.2684

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