Polymer–Metal–Organic\nFrameworks (polyMOFs)\nBased on Tailor-Made Poly(alkenamer)s

Polymeric linkers used to construct porous, crystalline\npolymer–metal–organic\nframeworks (polyMOFs) are predominantly based on macromolecules with\nmetal-coordinating ligand units (e.g., 1,4-benzenedicarboxylic acid,\nH<sub>2</sub>bdc) included in the primary polymer backbone. Polymers\nwith ligand units as pendants or dangling side chain substituents\nhave been far less explored for the synthesis of polyMOFs, despite\nthe fact that such systems may have distinct properties and could\ntake advantage of a variety of chain polymerization methods. Prevailing\nreports are based on nonliving polymerized linkers with H<sub>2</sub>bdc pendants that generated polyMOFs with key shortcomings in controlling\nthe polymerization, tailoring polymeric linker composition and polyMOF\nproperties, accessing porosity, etc. Herein, polymers containing\nH<sub>2</sub>bdc units as pendants were designed and synthesized via\ncontrolled olefin-metathesis polymerization. These poly(alkenamer)s\nwere subsequently assembled into porous, crystalline networks with\nan isoreticular MOF (IRMOF) lattice topology. These polymer architectures\nand polymerization methodologies provide access to the formation of\npolyMOFs with tailored characteristics, including controlled composition,\nnarrow dispersity, and side chain functionalization.