In Situ Encapsulation of Atomically Precise Nanoclusters in Reticular Frameworks via Mechanochemical Synthesis

Abstract The combination of atomically precise nanoclusters (APNCs) and reticular frameworks is promising for generating component‐specific nanocomposites with emergent properties. However, traditional liquid‐phase synthesis often hampers this potential by damaging APNCs and limiting combination diversity. Here, mechanochemical synthesis to explore the encapsulation of diverse oil‐ and water‐soluble APNCs within various reticular frameworks is employed, establishing a database of 21 unique APNC−framework combinations, including metal−organic frameworks (MOFs), covalent−organic frameworks (COFs), hydrogen−bonded organic frameworks (HOFs), and multivariate MOFs. These framework coatings not only spatially immobilize APNCs but also secure their structures, preventing aggregation and degradation while enhancing stability and activity. Encapsulating Au 25 in HOFs resulted in a remarkable 315‐fold increase in catalytic activity compared to Au 25 homogeneous catalyst, highlighting the framework's crucial role in catalytic enhancement. The mechanochemical synthesis strategy facilitates tailored support screening, catering to specific needs, and shows promise for developing multifunctional systems, including enzyme−APNC@frameworks material for cascade reactions.