Reversible Anion Exchange and Catalytic Properties of Two Cationic Metal-Organic Frameworks Based on Cu(I) and Ag(I)

We report the synthesis and characterization of two Ag(I)/Cu(I)-based cationic metal-organic frameworks and their application in both heterogeneous catalysis and anion exchange. The Cu(I)-based material was designed from our previously reported Ag(I) cationic topology. Both structures consist of cationic layers with pi-pi stacked chains of alternating metal and 4,4'-bipyridine. alpha,omega-Alkanedisulfonate serves as an anionic template, electrostatically bonding to the cationic layers. Due to weak interaction between the sulfonate template and cationic extended framework, both materials display reversible anion exchange for a variety of inorganic species. Indeed, the Ag(I)-based material exhibits highly efficient uptake of permanganate and perrhenate anion trapping, a model for pertechnetate trapping. The materials also display heterogeneous Lewis acidity, likely due to the coordinatively unsaturated metal sites which only bind to two bipy nitrogens and a weak interaction with one sulfonate oxygen. A comparative study on the influence of structure versus size selectivity and reusability for both exchange and catalysis is discussed.