Anion Binding as a Strategy for the Synthesis of Porous Salts

Porous salts have recently emerged as a promising new class of ultratunable permanently microporous solids. These adsorbents, which were first reported as ionic solids based on porous cations and anions, can be isolated from a wide variety of charged, permanently porous coordination cages. A challenge in realizing the full tunability of such systems, however, lies in the fact that the majority of coordination cages for which surface areas have been reported are comprised of charge-balanced inorganic and organic building blocks that result in neutral cages. As such, most reported permanently porous coordination cages cannot be used as reagents in the synthesis of porous salts. Here, we show that the facile reaction of TBAX (TBA⁺ = tetra-n-butylammonium; X = F^- and Cl^-) with molybdenum paddlewheel-based coordination cages of the M₄L₄ and M₂₄L₂₄ lantern and cuboctahedra structure types, respectively, affords charged cages by virtue of coordination of halide anions to the internal and/or external metal sites on these structures, as confirmed by single-crystal X-ray diffraction, X-ray photoelectron spectroscopy, and nuclear magnetic resonance (NMR) spectroscopy. At a practical level, the TBAX/cage reactions, which are fully reversible upon isolation of the cage with the appropriate solvent, solubilize otherwise rigorously insoluble cages. This method significantly increases the solution processability of these highly porous solids. Toward the formation of new porous salts, halide binding also serves to incorporate charge on neutral cages and make them amenable to simple salt metathesis reactions to afford new porous salts based on anions and cations with intrinsic porosity. A combination of diffraction methods and a suite of spectroscopic tools confirms speciation of the isolated solids, which represent a new class of highly tunable porous salts. Ultimately, this work represents a roadmap for the preparation of new porous solids and showcases the utility and broad applicability of anion binding as a strategy for the synthesis of porous salts.