Journal
NATURE CHEMISTRY
Volume 9, Issue 5, Pages 493-499Publisher
NATURE PUBLISHING GROUP
DOI: 10.1038/NCHEM.2684
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Funding
- KAKENHI [15H05483]
- Ministry of Education, Culture, Sports, Science and Technology, Japan [26102009, 26102011, 16H00787]
- Japan Society for the Promotion of Science [16J02156]
- Sekisui Chemical Grant Program
- Grants-in-Aid for Scientific Research [16J02156, 26249145, 16H00787, 26102011, 26102009, 15H05483] Funding Source: KAKEN
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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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