Despite numerous reports on nucleated supramolecular polymerization, the molecular origin of the properties of these supramolecular polymers remains overlooked. Here, the formation of fibers formed by self-assembly of N,N′,N′′-tris(alkoxybenzyl)benzene-1,3,5-tricarboxamides (benzyl-BTAs) has been studied using both simulations and experimental techniques. The simulations show that the fibers exhibit a dynamic behavior with stacking defects that appear and propagate differently depending on the BTA molecular structure. To validate theoretical results, a library of eight benzyl-BTAs has been synthesized to compare their supramolecular polymerizations both in the bulk and in apolar solvents. We show that the molecular organization of monomers and dynamics of supramolecular polymers strongly depend on the number and position of the alkoxy substituents on peripheral phenyl rings. By combining theoretical results with experimental measurements, we elucidate the likely role of competitive hydrogen bonding between the central amides and peripheral ether moieties on the stacking behavior of BTAs and the dynamics of structural defects in supramolecular polymers. Our findings open up new design rules for these dynamic materials.

中文翻译：

---

三苄基苯-1,3,5-三羧酸酰胺的超分子聚合中的竞争性氢键

尽管有关于成核的超分子聚合的大量报道，但是这些超分子聚合物的性质的分子起源仍然被忽略。在此，通过N，N '，N的自组装形成的纤维的形成使用模拟和实验技术研究了''-三（烷氧基苄基）苯-1,3,5-三甲酰胺（苄基-BTA）。模拟表明，纤维表现出动态行为，具有堆叠缺陷，该缺陷会根据BTA分子结构而出现和传播不同。为了验证理论结果，已经合成了八个苄基-BTA的文库，以比较它们在本体和非极性溶剂中的超分子聚合。我们表明，单体的分子组织和超分子聚合物的动力学很大程度上取决于周边苯环上烷氧基取代基的数量和位置。通过将理论结果与实验测量结果结合起来，我们阐明了中央酰胺和外围醚部分之间竞争性氢键对BTA堆积行为和超分子聚合物结构缺陷动力学的可能作用。我们的发现为这些动态材料开辟了新的设计规则。