Radical PolyMOFs: A Role for Ligand Dispersity in Enabling Crystallinity

Metal–organic frameworks (MOFs) derived from polymeric ligands (“polyMOFs”) have been prepared from a limited set of polymerization methods. Herein, we report the synthesis of polyMOF ligands featuring MOF-forming benzenedicarboxylic acid (H₂bdc) linkers on their sidechains using common radical polymerization techniques: reversible addition fragmentation chain transfer (RAFT) polymerization and free radical polymerization (FRP). Interestingly, high-dispersity ligands prepared through FRP formed crystalline polyMOFs while low-dispersity ligands prepared through RAFT required the addition of free H₂bdc to yield crystalline materials analogous to MOF-5 (Zn) and UiO-66 (Zr). This work opens new opportunities for the development of next-generation polymer–MOF hybrids based on radical polymerization and suggests that ligand dispersity is a key design parameter for polyMOF synthesis.