Network Flexibility: Control of Gate Opening in an Isostructural Series of Ag-MOFs by Linker Substitution

An isostructural series of 15 structurally flexible microporous silver metal–organic frameworks (MOFs) is presented. The compounds with a dinuclear silver core as secondary building unit (Ag₂N₄) can be obtained under solvothermal conditions from substituted triazolyl benzoate linkers and AgNO₃ or Ag₂SO₄; they exhibit 2-fold network interpenetration with lvt topology. Besides the crystal structures, the calculated pore size distributions of the microporous MOFs are reported. Simultaneous thermal analyses confirm the stability of the compounds up to 250 °C. Interconnected pores result in a three-dimensional pore structure. Although the porosity of the novel coordination polymers is in the range of only 20–36%, this series can be regarded as a model system for investigation of network flexibility, since the pore diameters and volumes can be gradually adjusted by the substituents of the 3-(1,2,4-triazol-4-yl)-5-benzamidobenzoates. The pore volumes of selected materials are experimentally determined by nitrogen adsorption at 77 K and carbon dioxide adsorption at room temperature. On the basis of the flexible behavior of the linkers a reversible framework transformation of the 2-fold interpenetrated network is observed. The resulting adsorption isotherms with one or two hysteresis loops are interpreted by a gate-opening process. Due to external stimuli, namely, the adsorptive pressure, the materials undergo a phase transition confirming the structural flexibility of the porous coordination polymer.