Isomeric Scandium-Organic Frameworks with High Hydrolytic Stability and Selective Adsorption of Acetylene

Two solvent-controlled topological isomers of scandium-organic frameworks [Sc(Hpzc)(pzc)]·DMF·2H₂O (1·DMF·2H₂O) and [Sc(Hpzc)(pzc)]·DMA·4H₂O (2·DMA·4H₂O) were synthesized using 2,5-pyrazinedicarboxylate (pzc^2-) (DMF = dimethylformamide; DMA = dimethylacetamide). Despite the isomeric nature of the obtained metal-organic frameworks (MOFs), they possess different structural features and unique adsorption properties toward gases and iodine. The compound 1 has widely spread among MOF structures a dia topology with ultranarrow channels, which together with inner surface functionalization leads to enhanced CO₂ adsorption and high selectivity factors in CO₂/CH₄ and CO₂/N₂ gas mixtures (25.9 and 35.6, respectively, 1/1 v/v). Moreover, a rare preferable adsorption of CO₂ over C₂H₂ was demonstrated. The biporous isomeric framework 2 has a crb topology inherent in zeolites. A remarkable adsorption affinity to C₂H₂ with the ideal adsorbed solution theory selectivity factor of 127.1 for a C₂H₂/C₂H₄ mixture (1/99 v/v) was achieved for 2. Both compounds have exceptional chemical stability in a wide range of pH from acidic to basic media.