4 years ago

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

Control over differentiation of a metastable supramolecular assembly in one and two dimensions
Tsuneaki Sakurai, Shu Seki, Masayuki Takeuchi, Kazunori Sugiyasu, Tomoya Fukui, Shinnosuke Kawai, Yoshitaka Matsushita, Takeshi Yasuda, Satoko Fujinuma
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.

Publisher URL: http://dx.doi.org/10.1038/nchem.2684

DOI: 10.1038/nchem.2684

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