Unlocking Advanced Architectures of Single‐Crystal Metal–Organic Frameworks

Abstract The synthesis of metal–organic frameworks (MOFs) with diverse geometries has captivated considerable interest due to their manifestation of novel and extraordinary properties. While much progress has been made in shaping regular polyhedral single‐crystal MOFs, the creation of more complex, topologically intricate nanostructures remains a largely unexplored frontier. Here, we present a refined site‐specific anisotropic assembly and etching co‐mediation approach to fabricate a series of hierarchical MOF nanohybrids and single‐crystal MOFs. This approach yields ZIF‐8&mSiO 2 nanohybrids with diverse topologies, alongside derived single‐crystal MOF nanoparticles exhibiting intricate morphologies such as hexapods, nested nanocages, and octopods. Our method involves the selective growth of six mSiO 2 nanoplates on the {100} facets of ZIF‐8 nanocubes, forming the cubic‐shaped ZIF‐8&mSiO 2 nanohybrids, with the concurrent etching of the {110} facets of initial ZIF‐8 nanocubes. By fine‐tuning this balance between the growth and etching, we achieved precise morphological control, transforming cubic nanohybrids into intricate hexapods nanohybrids. Additionally, secondary epitaxial growth of homo‐ or hetero‐MOFs on these hybrids led to ZIF‐8&mSiO 2 &MOF composites with six mSiO 2 inlays. Finally, selective alkaline etching of the mSiO 2 compartments result in single‐crystal MOF nanoparticles with unprecedented and sophisticated morphologies, such as hexapods, nested nanocages, octopods. This work advances the field of MOF nanostructure design, opening new avenues for the development of sophisticated, multifunctional materials.