Gate Opening without Volume Change Triggers Cooperative Gas Interactions, Underpins an Isotherm Step in Metal-Organic Frameworks.

Three halogenated metal-organic frameworks (MOFs) reported recently exhibited a second step in their CO 2 gas adsorption isotherms. The emergence of halogen-bonding interactions beyond a threshold gas pressure between the framework halogen and the CO 2 guest was conjectured to be the underlying reason for the additional step in the isotherm. Our investigation employing periodic density functional theory calculations did not show significant interactions between the halogen and CO 2 molecules. Further, using a combination of DFT-based ab initio molecular dynamics and grand canonical Monte Carlo simulations, we find that the increased separation of framework nitrate pairs facing each other across the pore channel enables the accommodation of an additional CO 2 molecule which is further stabilized by cooperative interactions─an observation that facilely explains the second isotherm step. The increased separation between the nitrate groups can occur without any lattice expansion, consistent with experiments. The results point to a structural feature to achieve this isotherm step in MOFs that neither possess large pores nor exhibit large-scale structural changes such as breathing.