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Rapid Cs<sup>+</sup> Capture via Multiple Supramolecular Interactions in Anionic Metal–Organic Framework Isomers

Kangwoo Jin, Xue‐Qian Wu, Ying‐Pin Chen, In‐Hyeok Park, Jian‐Rong Li, Jinhee Park

2022Inorganic Chemistry14 citationsDOIOpen Access PDF

Abstract

Metal–organic frameworks (MOFs) provide an ideal platform for ion exchange due to their high porosity and structural designability; however, developing MOFs that have the essential characteristics for ion exchange remains a challenge. These crucial features include fast kinetics, selectivity, and stability. We present two anionic isomers, DGIST-2 (2D) and DGIST-3 (3D), comprising distinctly arranged 5-(1,8-naphthalimido)isophthalate ligands and In3+ cations. Interestingly, in protic solvents, DGIST-2 transforms into a hydrolytically stable crystalline phase, DGIST-2′. DGIST-2′ and DGIST-3 exhibit rapid Cs+ adsorption kinetics, as well as high Cs+ affinity in the presence of competing cations. The mechanism for rapid and selective sorption is explored based on the results of single-crystal X-ray diffraction analysis of Cs+-incorporated DGIST-3. In Cs+-containing solutions, the loosely incorporated dimethylammonium countercation of the anionic framework is replaced by Cs+, which is held in the hydrophobic cavity by supramolecular ion–ion and cation−π interactions.

Topics & Concepts

ChemistrySupramolecular chemistrySorptionAdsorptionKineticsMetal-organic frameworkIon exchangeSelectivityIonInorganic chemistryCrystallographyPhysical chemistryCrystal structureOrganic chemistryCatalysisPhysicsQuantum mechanicsChemical Synthesis and CharacterizationMetal-Organic Frameworks: Synthesis and ApplicationsRadioactive element chemistry and processing