Double network hydrogels are composed of chemical and physical bonds, whose influences on the macroscopic material properties are convoluted. To decouple these, a model dually crosslinked network with independently tunable permanent and reversible crosslinks is introduced. This is realized by interlinking linear and tetra‐arm poly(ethylenegycol) (PEG) precursors with complementary reactive terminal groups. The former also carries a terpyridine ligand at each end, which forms reversible metallo‐supramolecular bonds upon addition of metal ions. These dual networks display different types and amounts of network defects, as studied by light scattering and proton double‐quantum (DQ) NMR. Dynamic light scattering suggests that the network mesh size decreases upon introduction of metal ions, as supported by a decrease of the residual dipolar coupling constant in NMR. Static light scattering indicates larger static inhomogeneities in those networks composed of stronger ions. This is complemented by a fast solid‐like component in the DQ buildup in NMR, attributed to the formation of nanoscopic clusters of charged complexes. The DQ buildup curves also suggest that the presence of strong physical bonds increases the fraction of mobile segments, like loops and dangling ends. This combined study unveils the interplay of chemical and physical bonds toward the formation of a hierarchical structure.

中文翻译：

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金属超分子双网络水凝胶模型中的连通性缺陷和集体组装

双网络水凝胶由化学键和物理键组成，其对宏观材料性能的影响是复杂的。为了消除这些耦合，引入了具有独立可调的永久性和可逆性交联的双交联模型网络。这是通过将线性和四臂聚乙二醇（PEG）前体与互补的反应性端基相互连接来实现的。前者在每个末端还带有一个吡啶吡啶配体，后者在添加金属离子后形成可逆的金属超分子键。根据光散射和质子双量子（DQ）NMR的研究，这些双重网络显示出不同类型和数量的网络缺陷。动态光散射表明，随着金属离子的引入，网络的网格尺寸减小，NMR中残留的偶极偶合常数的降低证实了该化合物的存在。静态光散射表明，在由强离子组成的网络中，较大的静态不均匀性。NMR中DQ积聚中的快速固体状成分对此起到了补充作用，这归因于带电配合物的纳米级簇的形成。DQ累积曲线还表明，强大的物理键的存在会增加可移动部分（如环和悬空末端）的比例。这项综合研究揭示了化学键和物理键对层次结构形成的相互作用。归因于带电配合物的纳米簇的形成。DQ累积曲线还表明，强大的物理键的存在会增加可移动部分（如环和悬空末端）的比例。这项联合研究揭示了化学键和物理键对层次结构形成的相互作用。归因于带电配合物的纳米簇的形成。DQ累积曲线还表明，强大的物理键的存在会增加可移动部分（如环和悬空末端）的比例。这项联合研究揭示了化学键和物理键对层次结构形成的相互作用。