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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., (© 2025 Wiley-VCH GmbH.)

Emulsion interface engineering has been widely employed for the synthesis of nanomaterials with various morphologies. However, the instability of the liquid-liquid interface and uncertain interfacial interactions impose significant limitations on controllable fabrications. Here, we developed a liquid-nano-liquid interface-oriented anisotropic encapsulation strategy for fabricating asymmetric nanohybrids. Specifically, functional nanoparticles such as magnetic nanoparticles, lanthanide fluorescent nanoparticles, and Au nanorods were anisotropically encapsulated by mesoporous polydopamine (mPDA). In this emulsion system, the wetting behavior of functional nanoparticles at the water/oil interface could be manipulated by the stabilizer of the emulsion (surfactant), leading to the anisotropic assembly of mPDA shell and resulting in various nanostructures, including core-shell, yolk-shell with small opening, ball-in-bowl, and multipetal structures. Due to their structural asymmetry, inherent magnetic properties, and photothermal properties, the ball-in-bowl structured Fe 3 O 4 @SiO 2 &mPDA nanohybrids, serving as proof of concept for nanomotors, demonstrated effective penetration of bacterial biofilm and promotion of infected wound healing. Overall, our approach offers a different perspective for designing morphologically controllable asymmetric structures based on liquid-nano-liquid interface in microemulsion systems that hold great potential for establishing innovative functional nanomaterials., Competing Interests: Competing interests statement:The authors declare no competing interest.