Selective CO₂ Sorption Using Compartmentalized Coordination Polymers with Discrete Voids*

Carbon capture and storage with porous materials is one of the most promising technologies to minimize CO₂ release into the atmosphere. Here, we report a family of compartmentalized coordination polymers (CCPs) capable of capturing gas molecules in a selective manner based on two novel tetrazole-based ligands. Crystal structures have been modelled theoretically under the Density Functional Theory (DFT) revealing the presence of discrete voids of 380 ų . Single gas adsorption isotherms of N₂ , CH₄ and CO₂ have been measured, obtaining a loading capacity of 0.6, 1.7 and 2.2 molecules/void at 10 bar and at 298 K for the best performing material. Moreover, they present excellent selectivity and regenerability for CO₂ in mixtures with CH₄ and N₂ in comparison with other reported materials, as evidenced by dynamic breakthrough gas experiments. These frameworks are therefore great candidates for separation of gas mixtures in the chemical engineering industry.