Simulating Assembly Landscapes for Comprehensive Understanding of Supramolecular Polymer–Solvent Systems,Journal of the American Chemical Society

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Simulating Assembly Landscapes for Comprehensive Understanding of Supramolecular Polymer–Solvent Systems
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-02-09 , DOI: 10.1021/jacs.2c12941
Stef A H Jansen _{1,

2} , Elisabeth Weyandt _{1,

2} , Tsubasa Aoki ₃ , Takayoshi Akiyama ₃ , Yoshimitsu Itoh ₃ , Ghislaine Vantomme _{1,

2} , Takuzo Aida _{3,

4} , E W Meijer _{1,

2,

5}

Affiliation

Complexity in supramolecular polymer systems arises from interactions between different components, including solvent molecules. By varying their concentration or temperature in such multicomponent systems, complex phenomena can occur such as thermally bisignate and dilution-induced assembly of supramolecular polymers. Herein, we demonstrate that both these phenomena emerge from the same underlying interaction mechanism between the components. As a model system, amide-decorated supramolecular polymers of porphyrins were investigated in combination with aliphatic alcohols as hydrogen-bond scavengers, and thermodynamic mass-balance models were applied to map the three-dimensional assembly landscapes. These studies unveiled that the interaction between hydrogen-bond scavengers and monomers is temperature-dependent and becomes dominant at high monomer concentrations. With these insights, we could exploit competitive monomer–alcohol interactions to prompt the dilution-induced assembly of various common monomers as well as bisignate assembly events. Moreover, kinetic insights were obtained by navigating through the assembly landscape. Similar to phase diagrams of covalent polymers, these assembly landscapes provide a comprehensive picture of supramolecular polymerizations, which helps to precisely regulate the system properties. The generality of this approach using assembly landscapes makes it relevant for any supramolecular system, and this enhanced control will open the door to build complex and functional supramolecular polymer systems.

中文翻译：

模拟组装景观以全面了解超分子聚合物-溶剂系统

超分子聚合物系统的复杂性源于不同组分（包括溶剂分子）之间的相互作用。通过改变此类多组分系统中的浓度或温度，可能会发生复杂的现象，例如超分子聚合物的热双联和稀释诱导的组装。在这里，我们证明这两种现象都是由组件之间相同的潜在相互作用机制产生的。作为模型系统，将酰胺修饰的卟啉超分子聚合物与作为氢键清除剂的脂肪醇结合起来进行研究，并应用热力学质量平衡模型来绘制三维组装图。这些研究揭示了氢键清除剂和单体之间的相互作用是温度依赖性的，并且在高单体浓度下变得占主导地位。有了这些见解，我们可以利用竞争性单体-醇相互作用来促进各种常见单体的稀释诱导组装以及双标记组装事件。此外，通过浏览装配环境获得了动力学见解。与共价聚合物的相图类似，这些组装图提供了超分子聚合的全面图景，这有助于精确调节系统性能。这种使用组装景观的方法的通用性使其适用于任何超分子系统，并且这种增强的控制将为构建复杂且功能性的超分子聚合物系统打开大门。

更新日期：2023-02-09

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