Superstructure‐Induced Hierarchical Assemblies for Nanoconfined Photocatalysis

Most attempts to synthesize supramolecular nanosystems are limited to a single mechanism, often resulting in the formation of nanomaterials that lack diversity in properties. Herein, hierarchical assemblies with appropriate variety are fabricated in bulk via a superstructure‐induced organic–inorganic hybrid strategy. The dynamic balance between substructures and superstructures is managed using covalent organic frameworks (COFs) and metal–organic frameworks (MOFs) as dual building blocks to regulate the performances of hierarchical assemblies. Significantly, the superstructures resulting from the controlled cascade between COFs and MOFs create highly active photocatalytic systems through multiple topologies. Our designed tandem photocatalysis can precisely and efficiently regulate the conversion rates of bioactive molecules (benzo[d]imidazoles) through competing redox pathways. Furthermore, benzo[d]imidazoles catalyzed by such supramolecular nanosystems can be isolated in yields ranging from 70 % to 93 % within tens of minutes. The multilayered structural states within the supramolecular systems demonstrate the importance of hierarchical assemblies in facilitating photocatalytic propagation and expanding the structural repertoire of supramolecular hybrids. Organic‐inorganic assemblies based on pillararene‐strutted covalent organic frameworks (COFs) have been developed as highly efficient photocatalysts for the synthesis of bioactive molecules (benzo[d]imidazoles). The pillararenes in the assemblies play an important role in enhancing the photocatalytic efficiency, thus providing valuable insights into the construction of multifunctional porous materials with innovative and designable functions.