Advantages of MOFs, COFs, and POPs over other 2D/3D materials and hybrids as heterogeneous catalysts for C[sbnd]H bond activation and functionalization

This article explores recent advancements in C[sbnd]H activation and functionalization reactions, which are key processes in organic synthesis that convert typically inert C[sbnd]H bonds into valuable functional groups. These transformations often require highly active and selective catalysts. Framework-based porous materials, particularly metal-organic frameworks (MOFs), covalent-organic frameworks (COFs), and porous organic polymers (POPs), including conjugated microporous polymers (CMPs), polymers of intrinsic microporosity (PIMs), porous aromatic frameworks (PAFs), and hyper-crosslinked polymers (HCPs), are emerging as promising heterogeneous catalysts. Their structural tunability, high surface area, and well-defined active sites provide major advantages. Tailored architectures enable precise control over metal nodes and organic linkers, enhancing activity and selectivity. The porous structure supports substrate diffusion, while rigid frameworks stabilize intermediates and minimize side reactions. These materials also support green chemistry principles due to reusability and operation under mild conditions. The review highlights strategies for modifying metal centers, linkers, and pore structures to improve performance. This article describes the benefits of using MOFs, POPs, and COFs with other 2D/3D and hybrid materials, including graphene- and silica-supported systems. Additionally, the review outlines current challenges, compares performance with traditional catalysts, and identifies opportunities for future research in C[sbnd]H activation and functionalization using framework-based porous materials.