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

Abstract 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, Co 3 ‐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 C 2 H 2 uptake capacity (200 cm 3 /g at 298 K), also exhibits (desirably) the lowest CO 2 uptake and hence the highest C 2 H 2 /CO 2 selectivity. The successful boost in both C 2 H 2 capacity and IAST selectivity allows Co 3 ‐cpt‐tph‐Cl to rank among the best crystalline porous materials, ionic MOFs in particular, for C 2 H 2 uptake and C 2 H 2 /CO 2 experimental breakthrough separation.