Simultaneous Control of Pore‐Space Partition and Charge Distribution in Multi‐Modular Metal–Organic Frameworks

We report here a strategy for making anionic pacs type porous materials by combining pore space partition with charge reallocation. The method uses the first negatively charged pore partition ligand (2,5,8-tri-(4-pyridyl)-1,3,4,6,7,9-hexaazaphenalene, H-tph) that simultaneously enables pore partition and charge reallocation. Over two dozen anionic pacs materials have been made to demonstrate their excellent chemical stability and a high degree of tunability. Notably, Ni₃ -bdt-tph (bdt=1,4-benzeneditetrazolate) exhibits month-long water stability, while CoV-bdt-tph sets a new benchmark for C₂ H₂ storage capacity under ambient conditions for ionic MOFs. In addition to tunable in-framework modules, we show feasibility to tune the type and concentration of extra-framework counter cations and their influence on both stability and capability to separate industrial C₃ H₈ /C₃ H₆ and C₆ H₆ /C₆ H₁₂ mixtures.