Isoreticular Contraction in Dicopper Paddle‐Wheel‐Based Metal‐Organic Frameworks to Enhance C2H2/CO2 Separation

Abstract Achieving a balance between high selectivity and uptake is a formidable challenge for the purification of acetylene from mixtures with carbon dioxide, particularly when seeking to maximize both C 2 H 2 adsorption capacity and C 2 H 2 /CO 2 separation selectivity in crystalline porous materials. In this study, leveraging the principles of reticular chemistry, we selected two tetracarboxylate‐based linkers and combined them with Cu 2+ ions to synthesize two isoreticular dicopper paddle‐wheel‐based metal‐organic frameworks (MOFs): Cu‐TPTC (terphenyl‐3,3’,5,5’‐tetracarboxylic acid, H 4 TPTC) and Cu‐ABTC (3,3,5,5‐azobenzenetetracarboxylic acid, H 4 ABTC). The structural and sorption analyses revealed that Cu‐ABTC, despite having slightly smaller pores due to the strategic replacement of a phenyl ring with an azo group between two tetratopic ligands, maintains high porosity compared to Cu‐TPTC. Furthermore, Cu‐ABTC outperforms Cu‐TPTC in terms of C 2 H 2 adsorption capacity (196 cm 3 g −1 at 298 K and 1 bar) and C 2 H 2 /CO 2 separation selectivity (16.5~5.6). These findings were corroborated by dynamic breakthrough experiments and computational modeling. This research highlights the potential of the isoreticular contraction strategy in enhancing MOFs for sophisticated gas adsorption and separation processes.