Pathway Complexity Versus Hierarchical Self-Assembly in N-Annulated Perylenes: Structural Effects in Seeded Supramolecular Polymerization
Pathway Complexity Versus Hierarchical Self-Assembly in N-Annulated Perylenes: Structural Effects in Seeded Supramolecular Polymerization
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DOI：
10.1002/anie.201801575
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发表时间：
2018-04-16
影响因子：
16.6
通讯作者：
Sanchez, Luis
中科院分区：
文献类型：
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作者：
Greciano, Elisa E.;Matarranz, Beatriz;Sanchez, Luis
对N-环戊烯1-3的分级自组装与途径复杂性进行了研究，它们的不同之处只在于连接perenencore和侧烷氧基链的连接基的性质。尽管结构相似，但化合物1和2在自组装方面表现出明显的差异。虽然1形成一个非路径聚集体I，它随着时间的推移(或通过添加种子)转化为热力学上的路径上产物，但2经历了一个分级过程，在这个过程中，动力学捕获的单体物种不会导致动力学控制的超分子生长。最后，化合物3缺乏酰胺基团，不能在相同的实验条件下自组装，并突出了酰胺基团及其在控制自组装途径中的地位的关键相关性。
Studies were carried out on the hierarchical self-assembly versus pathway complexity of N-annulated perylenes 1-3, which differ only in the nature of the linking groups connecting the perylene core and the side alkoxy chains. Despite the structural similarity, compounds 1 and 2 exhibit noticeable differences in their self-assembly. Whereas 1 forms an off-pathway aggregate I that converts over time (or by addition of seeds) into the thermodynamic, on-pathway product, 2 undergoes a hierarchical process in which the kinetically trapped monomer species does not lead to a kinetically controlled supramolecular growth. Finally, compound 3, which lacks the amide groups, is unable to self-assemble under identical experimental conditions and highlights the key relevance of the amide groups and their position to govern the self-assembly pathways.