New Supercage Metal–Organic Framework Based on Allopurinol Ligands Showing Acetylene Storage and Separation

To develop efficient adsorbent materials for storage and separation of C 2 H 2 , an unprecedented supercage MOF, [Me 2 NH 2 ]⋅[Zn 3 (ALP)(TDC) 2.5 ]⋅3.5DMF⋅2 H 2 O ( 1 ) was constructed through medicinal molecule allopurinol (ALP) and S‐containing 2,5‐thiophenedicarboxylic acid (H 2 TDC). 1 contains a novel linear trinuclear cluster that is composed by ALP and carboxylates and forms a final uncommon 5‐connected yfy topological framework. The framework possesses three types of interlinked cages decorated by rich functional sites, and reveals not only high adsorption capacity for C 2 H 2 but also excellent selective separation for C 2 H 2 /CO 2 and C 2 H 2 /CH 4 at 298 K. Dynamic breakthrough experiments on C 2 H 2 /CO 2 (1:1) mixture and C 2 H 2 /CH 4 (1:1) mixture also demonstrated the potential of the material to separate C 2 H 2 from CO 2 or CH 4 mixtures. Molecular simulations were also studied to identify the different CO 2 ‐ and C 2 H 2 ‐ binding sites in 1 , such as carboxylate groups, S atoms and carbonyl groups.