Design, Synthesis And Characterization Of Metal Organic Skeletal Compounds With Novel Structure

In this paper, six new metal-organic frameworks have been designed and synthesized based on copper(Ⅱ) salts and flexible ligands 1-(3,5-bis((1H-1,2,4-triazol-1-yl)methyl)-2,4,6-trimethylbenzyl)-1H-1,2,4-triazole(ttt mb) and 1-(3-((1H-1,2,4-triazol-1-yl)methyl)-2,4,6-trimethylbenzyl)-1H-1,2,4-triazole (bttmb) via the hydrothermal synthesis method. These complexes were characterized by the X-ray diffraction, IR spectra, elemental analyses, thermogravimetric analysis.We have synthesized three copper(Ⅰ) clusters of Cu11(tttmb)2C11(H2O)6] (1), [Cu7(tttmb)2Br4Cl3]·3H2O(2), [Cu7(tttmb)2Br7·H2O] (3) by the reaction of copper(Ⅱ) salts (chloride and copper bromide) and tttmb via solvothermal synthesis. Their structures and properties were characterized. The solvent formic acid not only regulated the pH of the solution but also facilitated the simple metal ions to be complex clusters.The two 2D layer of [Cu(tttmb)(H2O)2(HCOO)2] (4) and [Cu3(tttmb)2Br6O6·H2O] (5) were synthesized by the same copper salts and ligands as the compounds 1-3. But their structures were absolutely different. It was found that thesolvent and temperature played important roles in deciding the framework of the metal-organic materials.A novel porous [Cu13(C9H3O6)8(CH3CN)4(H2O)13Cl2] (6) was synthesized by the reaction of copper sulfate and 1-(3-((1H-1,2,4-triazol-1-yl)methyl)-2,4,6-trimethylbenzyl)-1H-1,2,4-triazole (bttmb) and 1,3,5-benzoic acid (H3BTC) with hydrothermal synthesis method. The frameworks of the compound 6 is the same as HKUST-1, and the difference between of them is that the compound 6 contains a object molecule Cu(CH3CN)4Cl2. The structure and properties were characterized. We also discussed the adsorption properties of the compound 6.