Concurrent Enhancement of Acetylene Uptake Capacity and Selectivity by Progressive Core Expansion and Extra-Framework Anions in Pore-Space-Partitioned Metal-Organic Frameworks.

A multi-stage core-expansion method is proposed here as one component of the integrative binding-site/extender/core-expansion (BEC) strategy. The conceptual deconstruction of the partitioning ligand into three editable parts draws our focus onto progressive core expansion and allows the optimization of both acetylene uptake and selectivity. The effectiveness of this strategy is shown through a family of eight cationic pore-partitioned materials containing three different partitioning ligands and various counter anions. The optimized structure, Co3-cpt-tph-Cl (Hcpt = 4-(p-carboxyphenyl)-1,2,4-triazole, H-tph = (2,5,8-tri-(4-pyridyl)-1,3,4,6,7,9-hexaazaphenalene) with the largest surface area and highest C2H2 uptake capacity (200 cm3/g at 298 K), also exhibits (desirably) the lowest CO2 uptake and hence the highest C2H2/CO2 selectivity. The successful boost in both C2H2 capacity and IAST selectivity allows Co3-cpt-tph-Cl to rank among the best crystalline porous materials, ionic MOFs in particular, for C2H2 uptake and C2H2/CO2 experimental breakthrough separation.