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 4.8(2) 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, [Zn-2(atz)(2)(CO3)]center dot 3H(2)O (2), [Zn-4(atz)(4)(CO3)(ox)]center dot 3H(2)O (3, H(2)oX = oxalic acid), [Zn-2(atz)(2)(sca)] (4, H(2)sca = succinic acid), [Zn-2(atz)(2)(ada)] (5, H(2)ada adipic acid), [Zn-2(atz)(2)(sba)] (6, H(2)sba = subefic acid), [Zn-2(atz)(2)(aza)] (7, H(2)aza = azelaic acid), and [Zn-2(atz)(2)(sea)] (8, H(2)sea 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 N-2 adsorption measurements were analyzed for the porous 2 and 3.