A Tale of Two Trimers from Two Different Worlds: A COF‐Inspired Synthetic Strategy for Pore‐Space Partitioning of MOFs

The introduction of a symmetry- and size-matching pore-partitioning agent in the form of either a molecular ligand, such as 2,4,6-tri(4-pyridinyl)-1,3,5-triazine (tpt), or a metal-complex cluster, into the hexagonal channels of MIL-88/MOF-235-type (the acs net) to create pacs-type (partitioned acs) crystalline porous materials is an effective strategy to develop high-performance gas adsorbents. We have developed an integrated COF-MOF coassembly strategy as a new method for pore-space partitioning through the coassembly of [(M3 (OH)1-x (O)x (COO)6 ] MOF-type and [B3 O3 (py)3 ] COF-type trimers. With this strategy, the coordination-driven assembly of the acs framework occurred concurrently and synergistically with the COF-1-type condensation of pyridine-4-boronic acid into a C3 -symmetric trimeric boroxine molecule. The resulting boroxine-based pacs materials exhibited dramatically enhanced gas-sorption properties as compared to nonpartitioned acs-type materials and are among the most efficient NH3 -sorption materials.