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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.

We report a silver-based cationic metal−organic framework with two mixed organic linkers directing the structure. The structure consists of 1D Ag(4,4′-bipy) cationic chains arranged into close-packed layers. Weakly bound alkanedisulfonate anions charge-balance the layers, where only one oxygen of each sulfonate makes a long contact with the Ag. The unsaturated linear Ag centers likely allow the Lewis acidity displayed by the material for ketone protection as well as esterification. The material showed no reduction in yield after three catalytic runs with average 95% conversion yield for ketal formation and 57% for esterification without further water removal. In addition to hydrothermal conditions, the structure can be synthesized by reflux or room temperature, with almost identical catalytic ability. Other properties of this compound including chemical and thermal stability are also described.

We have discovered a rare example of a cationically charged inorganic material. The layered structure is an example outside the extensively studied isostructural set of anionic clays/layered double hydroxides and our previously reported lead fluoride nitrate. For the present compound, the antimony oxide hydroxide layers are positively charged and are templated by anionic alkylenedisulfonate. The organic molecules are only bonded electrostatically to the layers with sulfonate oxygen to antimony distances beyond the covalent range. The material catalyzes a ketal formation reaction as a Lewis acid without the need for drying the solvent before the reaction or a nonaqueous medium such as toluene. The catalyst is heterogeneous and is completely recovered after the catalysis for reapplication.

Two metal-organic frameworks containing barium were synthesized hydrothermally and investigated for their catalytic properties. Ba(2)F(2)[O(3)SC(2)H(4)SO(3)] has barium fluoride layers linked by organic 1,2-ethanedisulfonate molecules. Ba[O(3)SC(2)H(4)SO(3)] has discrete barium centers arranged in layers and connected covalently by ethanedisulfonate bridges. Thermogravimetric analysis showed that Ba(2)F(2)[O(3)SC(2)H(4)SO(3)] is stable to ca. 325 °C and Ba[O(3)SC(2)H(4)SO(3)] to ca. 375 °C. These materials expand the metal-organic frameworks available for group II metals bound to organodisulfonate linkers and are potentially useful for a range of heterogeneous acid catalysis reactions.