Assembly of crystallites into three-dimensional hierarchical superstructures is vital for the design of multicomponent architectures as capsules and reactors for storage, delivery, and catalysis. However, the development of these assemblies, for example, spherulite superstructures, has mainly been hampered by limited control over nucleation, orientational growth, and stability. In this work, we observed a hierarchical evolution from metal-organic framework (MOF) nanofibrils into spherulite superstructures. Under a polarized light, these superstructures exhibited a “Maltese cross” extinction pattern typical of spherulites, which is the first time this has been observed in porous materials. We demonstrated that by tuning the evolution kinetics via a mixed-solvent approach, varying morphologies could be obtained as a result of small-angle branching. Isoreticular expansion of MOF spherulites and incorporation of multiple components could also be achieved. This work provides a fresh avenue to pack porous crystallites into sophisticated superstructures, which are expected to serve applications from catalysis to guest delivery and transportation.

将微晶组装成三维层次的上层结构对于多组分体系结构的设计至关重要，这些体系结构是用于储存，输送和催化的胶囊和反应器。但是，这些组件（例如球晶上层结构）的发展主要受到成核，取向生长和稳定性的有限控制的阻碍。在这项工作中，我们观察到了从金属有机骨架（MOF）纳米原纤维到球晶上层结构的分层演化。在偏振光下，这些上部结构呈现出典型的球晶“马耳他十字”消光图案，这是首次在多孔材料中观察到。我们证明了通过使用混合溶剂方法调节演化动力学，由于小角度分支，可以获得不同的形态。也可以实现MOF球晶的等规膨胀和多种组分的结合。这项工作提供了将多孔微晶包装成复杂的上层结构的新途径，有望将其用于从催化到客体运输和运输的应用。