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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 C2H2 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 C3H8/C3H6 and C6H6/C6H12 mixtures. [ABSTRACT FROM AUTHOR]

For rare‐earth separation, selective crystallization into metal‐organic frameworks (MOFs) offers new opportunities. Especially important is the development of MOF platforms with high selectivity toward target ions. Here we report a MOF platform (CPM‐66) with low‐coordination‐number environment for rare‐earth ions. This platform is highly responsive to the size variation of rare‐earth ions and shows exceptional ion‐size selectivity during crystallization. CPM‐66 family are based on M3O trimers (M=6‐coordinated Sc, In, Er‐Lu) that are rare for lanthanides. We show that the size matching between urea‐type solvents and metal ions is crucial for their successful synthesis. We further show that CPM‐66 enables a dramatic multi‐fold increase in separation efficiency over CPM‐29 with 7‐coordinated ions. This work provides some insights into methods to prepare low‐coordinate MOFs from large ions and such MOFs could serve as high‐efficiency platforms for lanthanide separation, as well as other applications. [ABSTRACT FROM AUTHOR]

Reported herein are two new polymorphic Co-MOFs (CTGU-5 and -6) that can be selectively crystallized into the pure 2D or 3D net using an anionic or neutral surfactant, respectively. Each polymorph contains a H2O molecule, but differs dramatically in its bonding to the framework, which in turn affects the crystal structure and electrocatalytic performance for hydrogen evolution reaction (HER). Both experimental and computational studies find that 2D CTGU-5 which has coordinates water and more open access to the cobalt site has higher electrocatalytic activity than CTGU-6 with the lattice water. The integration with co-catalysts, such as acetylene black (AB) leads to a composite material, AB&CTGU-5 (1:4) with very efficient HER catalytic properties among reported MOFs. It exhibits superior HER properties including a very positive onset potential of 18 mV, low Tafel slope of 45 mV dec−1, higher exchange current density of 8.6×10−4 A cm−2, and long-term stability. [ABSTRACT FROM AUTHOR]