Supramolecular polymers based on host-guest molecular recognition have emerged as promising platforms for the development of smart materials. However, the studies on them are primarily conducted in solution and/or in the gel state. In contrast, little is known about dynamic properties and applications of supramolecular polymers in bulk. Herein, we present a self-crosslinking supramolecular polymer network (SPN) as a model system to understand the bulk properties controlled by noncovalent interactions. Specifically, the SPN monomer is composed of two benzo-21-crown-7 (B21C7) host units and two dialkylammonium salt guest moieties on a four-arm core, wherein complementary host-guest complexation drives the formation of the SPN with [2]pseudorotaxane linkages between B21C7 and ammonium motifs. The dynamic and reversible behaviors of the linkages are evaluated by measurement of viscoelasticity. The results indicate that the host-guest molecular recognition becomes highly dynamic at elevated temperature. Moreover, the relatively high activation energy of the SPN manifests itself as a new type of thermo-plastic material with network topology freezing glass transition. Finally, we demonstrate how these findings provide insights into the malleability and processability of the SPN by simple demos. The fundamental understanding gained from the research on this SPN in bulk will facilitate the advancement and application of supramolecular materials.

中文翻译：

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基于冠醚分子识别的自交联超分子聚合物网络

基于主客体分子识别的超分子聚合物已成为开发智能材料的有前途的平台。然而，对它们的研究主要是在溶液和/或凝胶状态下进行的。相比之下，对超分子聚合物的动态特性和应用知之甚少。在此，我们提出了一种自交联超分子聚合物网络 (SPN) 作为模型系统，以了解由非共价相互作用控制的整体特性。具体而言，SPN 单体由四臂核心上的两个苯并-21-冠-7 (B21C7) 主体单元和两个二烷基铵盐客体部分组成，其中互补的主客体复合驱动了 [2] B21C7 和铵基序之间的假轮烷键。通过测量粘弹性来评估连接的动态和可逆行为。结果表明主客体分子识别在升高的温度下变得高度动态。此外，SPN相对较高的活化能表现为一种新型的具有网络拓扑冻结玻璃化转变的热塑性材料。最后，我们展示了这些发现如何通过简单的演示深入了解 SPN 的延展性和可加工性。对这种SPN的批量研究获得的基本认识将促进超分子材料的进步和应用。SPN相对较高的活化能表现为一种新型的具有网络拓扑结构冻结玻璃化转变的热塑性材料。最后，我们展示了这些发现如何通过简单的演示深入了解 SPN 的延展性和可加工性。对这种SPN的批量研究获得的基本认识将促进超分子材料的进步和应用。SPN相对较高的活化能表现为一种新型的具有网络拓扑结构冻结玻璃化转变的热塑性材料。最后，我们展示了这些发现如何通过简单的演示深入了解 SPN 的延展性和可加工性。对这种SPN的批量研究获得的基本认识将促进超分子材料的进步和应用。