Synthesis and Applications of Porous Organosulfonate-Based Metal-Organic Frameworks

Metal-organic frameworks (MOFs) are an emerging class of porous crystalline materials attracting attention for their vast array of topologies as well as potential applications in gas storage, heterogeneous catalysis, and molecular sensing. In most cases, organocarboxylates (or corresponding carboxylic acids) are the most common building block, achieving well-defined metal-carboxylate coordination motifs in MOF structures. However, organosulfonates (or corresponding sulfonic acids) have been less well studied in MOF chemistry, probably owing to the weak coordination tendency of the sulfonate oxygens toward metal centers. This review summarizes the research on organosulfonate-based porous crystalline MOFs in recent years. The construction of most porous organosulfonate MOFs relies on using either a second N-donor ligand or carboxylate-sulfonate bifunctional ligands. Despite occupying more confined porosity than the carboxylate counterpart, the permanent porosity in organosulfonate MOFs is often highly polar and hydrophilic. Thus, organosulfonate MOFs often exhibit improved proton/Li⁺ conductivity as well as CO₂ affinity compared with their carboxylate-based counterparts. In addition, the application of organosulfonate MOFs in molecular sensing, molecular sieving, catalysis, and anion exchange are discussed in this review as well.