Advancing Porous Material Design: The Fusion of Metal-Organic and Covalent Organic Frameworks

January 27, 2025

Porous materials play a crucial role in diverse applications, including gas storage, separation, catalysis, and drug delivery. Recent advancements in metal–organic frameworks (MOFs) and covalent organic frameworks (COFs) have significantly broadened the scope of possibilities in this field. We have now introduced a novel class of hybrid materials called metal–organic–covalent–organic frameworks (MOCOFs), which seamlessly integrate the strengths of both MOFs and COFs.

MOFs and COFs are constructed through the self-assembly of molecular building blocks, distinguished by their bonding types—MOFs utilize coordination bonds between metal ions and organic ligands, while COFs rely on covalent bonds between organic molecules. Each bonding type offers distinct advantages but also presents challenges: MOFs often encounter issues with chemical stability, whereas COFs struggle with poor crystallinity, thus limiting their design and application potentials. The newly developed MOCOFs overcome these limitations by achieving both high crystallinity and chemical robustness through the dual extension of coordination and organic linkages.

The inaugural example of this new class, MOCOF-1, is synthesized from cobalt aminoporphyrin and dialdehydes, with amino groups participating in both cobalt coordination and imine condensation. MOCOF-1 boasts a crystal size reaching 100 µm, demonstrates durability against water and base, and presents an unprecedented chiral topology, showcasing the benefits of the double extension approach. It also exhibits desirable properties akin to MOFs and COFs: a substantial BET surface area of 2836 m²/g, the ability to adsorb acid molecules, and structural tunability to introduce various functional groups.

This study not only introduces MOCOFs as a new class of porous materials but also highlights the potential for a synergistic integration of MOF and COF chemistry. These findings pave the way for designing porous materials with customized properties and new topologies.

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