Abstract
A Cd(II)–organic framework {[Cd2(tpim)4(SO4)(H2O)2]·(SO4)·21H2O}n (1) was synthesized by reacting CdSO4·8/3H2O and 2,4,5-tri(4-pyridyl)imidazole (tpim) under hydrothermal conditions. A structural analysis showed that compound 1 adopts a layered structure in which the [Cd(tpim)2]n chains are linked by sulfate anions. These 2D layers are further packed into a 3D supramolecular framework via π–π interactions. The structure contains two types of SO42− anions, i.e., bridging SO42− and free SO42− anions, the latter of which are included in the large channels of the framework. Compound 1 exhibits interesting anion exchange behavior. In the presence of SCN− anions, both the bridging and free SO42− anions in 1 were completely exchanged by SCN− ligands to form a 1D species [Cd(tpim)2(SCN)2] (1A), in which the SCN– moieties function as a monodentate ligand. On the other hand, when compound 1 was ion exchanged with N3− anions in aqueous solution, the bridging SO42− moieties remained intact, and only the free guest SO42− were replaced by N3− anions. The gas adsorption behavior of the activated compound 1 was also investigated.
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