Abstract Understanding the influence of the molecular architecture on the self-assembly and properties of supramolecular organogel materials is necessary for elucidating the structure-property relationship. Although conventional gelation motifs (e.g., amides, long alkyl side chains, and steroidal groups) have been considered essential for the effective gel process, the lack of gelation motifs hinders the development and self-assembly of non-conventional gelators. Herein, coumarin-based derivatives (1–12) without a conventional gelation motif were designed and synthesised by inducing a one-step reaction that entails fine-tuning the molecular architecture, particularly the position of the nitrogen atom in pyridine, the substitution position of pyridine, and the placement of methyl in coumarin. A previous gelation study revealed that 7-substituted coumarin-based derivatives with methyl (1–4) are highly efficient gelators that can self-assemble to form different nanostructures, and gelate various polar protic solvents. After small-scale modification of the molecular structures, Derivatives 5–6 self-assembled and only formed gels in the alcohol phase, whereas gels were not formed by Derivatives 7–12 in various solvents. Interestingly, the fluorescence property of these gels was significantly influenced by the dielectric constant and viscosity of the solvent. Furthermore, differences in the self-assembly and fluorescence of gelators were numerically investigated by performing density functional theory calculations and all-atom molecular dynamics simulations. This study provides a foundation for the development of a low-cost, non-conventional supramolecular organogel system with minimal building blocks, a modifiable self-assembly pathway, and alterable properties.

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解读基于香豆素的超分子有机凝胶材料的结构-性能关系

摘要 了解分子结构对超分子有机凝胶材料自组装和性能的影响对于阐明结构-性能关系是必要的。尽管传统的凝胶基序（例如酰胺、长烷基侧链和甾族基团）被认为是有效凝胶过程必不可少的，但凝胶基序的缺乏阻碍了非常规凝胶剂的开发和自组装。在此，没有传统凝胶基序的香豆素衍生物（1-12）通过诱导一步反应设计和合成，该反应需要微调分子结构，特别是吡啶中氮原子的位置，取代位置吡啶，以及甲基在香豆素中的位置。先前的凝胶研究表明，具有甲基 (1-4) 的 7-取代香豆素基衍生物是高效的凝胶剂，可以自组装形成不同的纳米结构，并使各种极性质子溶剂凝胶化。在对分子结构进行小规模修饰后，衍生物 5-6 自组装并仅在醇相中形成凝胶，而衍生物 7-12 在各种溶剂中未形成凝胶。有趣的是，这些凝胶的荧光性质受溶剂的介电常数和粘度的显着影响。此外，通过执行密度泛函理论计算和全原子分子动力学模拟，对凝胶剂的自组装和荧光的差异进行了数值研究。本研究为开发低成本、