Superstructures with nanoscale building blocks, when coupled with precise control of the constituent units, open opportunities in rationally designing and manufacturing desired functional materials. Yet, synthetic strategies for the large-scale production of superstructures are scarce. We report a scalable and generalized approach to synthesizing superstructures assembled from atomically precise Ce₂₄O₂₈(OH)₈ and other rare-earth metal-oxide nanoclusters alongside a detailed description of the self-assembly mechanism. Combining operando small-angle X-ray scattering, ex situ molecular and structural characterizations, and molecular dynamics simulations indicates that a high-temperature ligand-switching mechanism, from oleate to benzoate, governs the formation of the nanocluster assembly. The chemical tuning of surface ligands controls superstructure disassembly and reassembly, and furthermore, enables the synthesis of multicomponent superstructures. This synthetic approach, and the accurate mechanistic understanding, are promising for the preparation of superstructures for use in electronics, plasmonics, magnetics and catalysis.

具有纳米级构建块的上层结构，加上对组成单元的精确控制，为合理设计和制造所需功能材料提供了机会。然而，用于大规模生产上层建筑的合成策略很少。_{我们报告了一种可扩展和通用的方法来合成由原子级精确的 Ce 24} O ₂₈ (OH) ₈组装的超结构和其他稀土金属氧化物纳米团簇以及自组装机制的详细描述。结合原位小角 X 射线散射、非原位分子和结构表征以及分子动力学模拟表明，从油酸到苯甲酸的高温配体转换机制控制着纳米团簇组装的形成。表面配体的化学调节控制超结构的分解和重组，以及更多，使多组分超结构的合成成为可能。这种合成方法和准确的机理理解有望用于制备用于电子、等离子体、磁学和催化的超结构。