Gas Sorption in Porous Ionic Packings (PIPs) Based on the Closo-dodecaborate anion

Porous ionic packings (PIPs) offer a novel strategy for designing functional porous materials using packed large spherical ions to create intrinsic, isolated voids within a crystal lattice. These materials exhibit accessible pores for small gases at moderate temperatures, despite the lack of pore interconnectivity. We demonstrate this concept with (NMe₄)₂B₁₂H₁₂, which adopts a face-centered cubic anti-CaF₂ structure. We speculate that the dynamic ion rotation facilitates gas diffusion, while polarized B–Hδ⁻ bonds enhance affinity to H2.