Pillaring Zn-Triazolate Layers with Flexible Aliphatic Dicarboxylates into Three-Dimensional Metal−Organic Frameworks

Solvothermal treatments of Zn(II) salts and 3-amino-1H-1,2,4-triazole in mixed water−dimethylformamide solvent produced a two-dimensional, wavy layer structure [Zn(atz)(fa)] (1, Hfa = formic acid) with a 4.82 Zn(atz) topology. While carbonate, oxalate, and aliphatic dicarboxylates are used to replace the terminal formate ligand, a series of three-dimensional pillared-layer metal−organic frameworks, namely, [Zn2(atz)2(CO3)]·3H2O (2), [Zn4(atz)4(CO3)(ox)]·3H2O (3, H2ox = oxalic acid), [Zn2(atz)2(sca)] (4, H2sca = succinic acid), [Zn2(atz)2(ada)] (5, H2ada = adipic acid), [Zn2(atz)2(sba)] (6, H2sba = suberic acid), [Zn2(atz)2(aza)] (7, H2aza = azelaic acid), and [Zn2(atz)2(sea)] (8, H2sea = sebacylic acid), are constructed. The crystal structural analyses demonstrate that the dicarboxylates have a significant impact on the Zn(atz) layers, which adopt various corrugated configurations in these three-dimensional metal−organic frameworks due to the different lengths and geometries of these pillars. Thermal stabilities of these compounds were examined by thermogravimetric analysis, while N2 adsorption measurements were analyzed for the porous 2 and 3.