Single‐Crystal Superstructures via Hierarchical Assemblies of Giant Rubik's Cubes as Tertiary Building Units

Abstract

AbstractIntricate superstructures possess unusual structural features and promising applications. The preparation of superstructures with single‐crystalline nature are conducive to understanding the structure–property relationship, however, remains an intriguing challenge. Herein we put forward a new hierarchical assembly strategy towards rational and precise construction of intricate single‐crystal superstructures. Firstly, two unprecedented superclusters in Rubik's cube's form with a size of ≈2×2×2 nm3are constructed by aggregation of eight {Pr4Sb12} oxohalide clusters as secondary building units (SBUs). Then, the Rubik's cubes further act as isolable tertiary building units (TBUs) to assemble diversified single‐crystal superstructures. Importantly, intermediate assembly states are captured, which helps illustrate the evolution of TBU‐based superstructures and thus provides a profound understanding of the assembly process of superstructures at the atomic level.