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
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DOI：
10.1038/nchem.2684
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发表时间：
2017-05-01
期刊：
影响因子：
21.8
通讯作者：
Sugiyasu, Kazunori
中科院分区：
文献类型：
--
作者：
Fukui, Tomoya;Kawai, Shinnosuke;Sugiyasu, Kazunori
在动力学控制下的分子自组装有望产生无法通过自发热力学过程获得的纳米结构。此外，与生物分子系统类似的依赖时间的进化可以在这种不平衡的条件下发生，从而允许合成具有增强复杂性的超分子组件。在这里，我们报告了亚稳态的卟啉超分子组装分化为纳米纤维和纳米片状结构的能力。对自组装中分子设计和途径复杂性之间关系的机械研究揭示了支配独特动力学行为的能量图景。基于这一认识，我们可以控制分化现象，并使用相同的单体实现一维和二维活性超分子聚合。此外，我们发现所得到的纳米结构在电子结构上是截然不同的，这说明了材料的性质依赖于路径。
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.