Selective nitrogen adsorption via backbonding in a metal-organic framework with exposed vanadium sites

Industrial processes prominently feature π-acidic gases, and an adsorbent capable of selectively interacting with these molecules could enable important chemical separations^1-4. Biological systems use accessible, reducing metal centres to bind and activate weakly π-acidic species, such as N₂, through backbonding interactions^5-7, and incorporating analogous moieties into a porous material should give rise to a similar adsorption mechanism for these gaseous substrates⁸. Here, we report a metal-organic framework featuring exposed vanadium(II) centres capable of back-donating electron density to weak π acids to successfully target π acidity for separation applications. This adsorption mechanism, together with a high concentration of available adsorption sites, results in record N₂ capacities and selectivities for the removal of N₂ from mixtures with CH₄, while further enabling olefin/paraffin separations at elevated temperatures. Ultimately, incorporating such π-basic metal centres into porous materials offers a handle for capturing and activating key molecular species within next-generation adsorbents.