Tunable Energy Landscapes to Control Pathway Complexity in Self‐Assembled N‐Heterotriangulenes: Living and Seeded Supramolecular Polymerization,Small

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Tunable Energy Landscapes to Control Pathway Complexity in Self‐Assembled N‐Heterotriangulenes: Living and Seeded Supramolecular Polymerization
Small ( IF 13.0 ) Pub Date : 2017-11-15 , DOI: 10.1002/smll.201702437
Jorge S. Valera ₁ , Rafael Gómez ₁ , Luis Sánchez ₁

Affiliation

Herein, the synthesis and self‐assembling features of N‐heterotriangulenes 1–3 decorated in their periphery with 3,4,5‐trialkoxy‐N‐(alkoxy)benzamide moieties that enable kinetic control of the supramolecular polymerization process are described. The selection of an appropriate solvent results in a tunable energy landscape in which the relative energy of the different monomeric or aggregated species can be regulated. Thus, in a methylcyclohexane/toluene (MCH/Tol) mixture, intramolecular hydrogen‐bonding interactions in the peripheral side units favor the formation of metastable inactivated monomers that evolve with time at precise conditions of concentration and temperature. A pathway complexity in the supramolecular polymerization of 1–3 cannot be determined in MCH/Tol mixtures but, importantly, this situation changes by using CCl₄. In this solvent, the off‐pathway product is a face‐to‐face H‐type aggregate and the on‐pathway product is the slipped face‐to‐face J‐type aggregate. The autocatalytic transformation of the metastable monomeric units, as well as the two competing off‐ and on‐pathway aggregates allow the realization of seeded and living supramolecular polymerizations. Interestingly, the presence of chiral, branched side chains in chiral (S)‐2 noticeably retards the kinetics of the investigated transformations. This work brings to light the relevance of controlling the pathway complexity in self‐assembling units and opens new avenues for the investigation of complex and functional supramolecular structures.

中文翻译：

可调节的能源格局可控制自组装N-异三角异构体中通路的复杂性：活性和种子超分子聚合

在此，合成和自组装功能Ñ -heterotriangulenes 1 - 3在其周边装饰有3,4,5-三烷氧基Ñ描述了能够动态控制超分子聚合过程的（烷氧基）苯甲酰胺部分。选择合适的溶剂会产生可调节的能量格局，在其中可以调节不同单体或聚集物种的相对能量。因此，在甲基环己烷/甲苯（MCH / Tol）混合物中，外围侧单元中的分子内氢键相互作用有助于形成亚稳灭活的单体，这些单体在精确的浓度和温度条件下会随时间发展。在超分子聚合的通路复杂1 - 3不能在MCH /托尔的混合物来确定，但重要的是，这种情况下，通过使用改变的CCl ₄。在这种溶剂中，路旁产品是面对面的H型骨料，路上产品是滑动的面对面J型骨料。亚稳态单体单元的自动催化转化，以及两种竞争性的非途中和途中聚集体，均可实现种子化和活性超分子聚合。有趣的是，手性（S）-2中存在手性，支链侧链会显着阻碍所研究转化的动力学。这项工作揭示了在自组装单元中控制路径复杂性的相关性，并为研究复杂和功能性超分子结构开辟了新途径。

更新日期：2017-11-15

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