Cyclobutanedicarboxylate Metal-Organic Frameworks as a Platform for Dramatic Amplification of Pore Partition Effect.

Ultrafine tuning of MOF structures at subangstrom or picometer levels can help improve separation selectivity for gases with subtle differences. However, for MOFs with a large enough pore size, the effect from ultrafine tuning on sorption can be muted. Here we show an integrative strategy that couples extreme pore compression with ultrafine pore tuning. This strategy is made possible by unique combination of two features of the partitioned acs (pacs) platform: multimodular framework and exceptional tolerance toward isoreticular replacement. Specifically, we use one module (ligand 1, L1) to shrink the pore size to an extreme minimum on pacs. A compression ratio of about 30% was achieved (based on the unit cell c/a ratio) from prototypical 1,4-benzenedicarboxylate-pacs to trans-1,3-cyclobutanedicarboxylate-pacs. This is followed by using another module (ligand 2, L2) for ultrafine pore tuning (<3% compression). This L1-L2 strategy increases the C2H2/CO2 selectivity from 2.6 to 20.8 and gives rise to an excellent experimental breakthrough performance. As the shortest cyclic dicarboxylate that mimics p-benzene-based moieties using a bioisosteric (BIS) strategy on pacs, trans-1,3-cyclobutanedicarboxylate offers new opportunities in MOF chemistry.