Synthetically trapping kinetically varied (super)structures of molecular assemblies and amplifying them to the macroscale is a promising, yet challenging, approach for the advancement of meta-stable materials. Here, we demonstrated a concerted kinetic trapping design to timely resolve a set of transient polypseudorotaxanes in solution and harness a crop of them via micro-crystallization. By installing stopper or speed bump moieties on the polymer axles, meta-stable polypseudorotaxanes with segmented cyclodextrin blocks were hierarchically amplified into crystalline networks of different crosslinking densities at mesoscale and viscoelastic hydrogels with 3D-printability in bulk. We demonstrated simultaneous 3D-printing of two polypseudorotaxane networks from one reactive ensemble and their conversion to heterogeneous polyrotaxane monoliths. Spatially programming the macroscale shapes of these heterogeneous polyrotaxanes enabled the construction of moisture-responsive actuators, in which the shape morphing originated from the different numbers of cyclodextrins interlocked in these polyrotaxane networks.

合成捕获分子组装的动力学变化（超）结构并将它们放大到宏观尺度是一种有前途但具有挑战性的方法，可用于亚稳态材料的进步。在这里，我们展示了协调一致的动力学捕获设计，以及时解决溶液中的一组瞬态多假轮烷，并通过微结晶利用其中的一批。通过在聚合物轴上安装塞子或减速块部分，具有分段环糊精嵌段的亚稳聚假轮烷被分级放大为不同交联密度的中尺度晶体网络和具有 3D 可打印性的粘弹性水凝胶。我们展示了从一个反应性集合中同时 3D 打印两个聚轮烷网络及其向异质聚轮烷整料的转化。