Macro-/mesoporous Metal–Organic Frameworks Templated by Amphiphilic Block Copolymers Enable Enhanced Uptake of Large Molecules

The first synthesis of hierarchical porous metal–organic frameworks (HP-MOFs) is reported through a solvent evaporation-induced co-assembly of polystyrene-block-poly(ethylene oxide) (PS-b-PEO) and MOF building blocks. The growth of MOFs is restricted to confined spaces formed by self-assembled PS-b-PEO, and mesopores and/or macropores are created after removing PS-b-PEO by solvent rinsing. This approach avoids phase separation and competitive interactions between templates and MOF building blocks. Both amorphous and crystalline HP-MOFs can be synthesized by finely controlling MOF growth conditions. Additionally, HP-MOFs (ZIF-L sheets) with honeycomb-like channels show significantly enhanced incorporation of large guest molecules compared to microporous MOFs. This study establishes an efficient synthetic strategy for preparing HP-MOFs with highly accessible mesopores and macropores for applications involving large molecules.