Syntheses, Structures And Properties Of Novel Metal-Organic Sulfonate Polymers

Synthesis, Structure and Properties of Novel Metal-Sulfonate PolymersMetal-organic polymers, as a kind of functional molecular material, have attracted much attention for their flexible tailoring, various topologies and promising application in ion-exchange, adsorption, molecular recognization, catalysts along with optics, electrics, magnetism and enantioselective separation. Metal-organic polymers with rigid open frameworks, zeolite-like materials, possess not only porous structures similar to inorganic zeolites but also better performance in gas sorption and store than traditional zeolites. At the same time, metal-organic polymers can be endowed with multifunctional properties by selecting functional metal ions and organic ligands with functional groups.According to the principle of molecular engineering, for the multifunctional properties of metal-organic polymers, we have focused our study on the synthesis, structures and multifunctional properties of metal-organic polymers with charming topologies. Carboxylate ligands have been widely studied because of strong coordination ability and varieties of coordination modes. However, studies on sulfonate ligands have been only attracted attention in recent years. In this dissertation, we choosing sulfonate as organic ligands and different metals as center atoms have prepared 11 new metal organic polymers through coordinative bonds or supramolecular weak interactions and analyzed their structures as well as explored their multifunctional properties, promising applications in optics, electric, magnetism, enantioselective separation and catalysis. These results will be introduced from the following three issues:First of all, realization of permanent porosity is the pre-requisite of porous metal organic polymers for their application in gas storage, separation and heterogeneous catalysis. People are pursuing the networks with the large channels and cavities, and at the same time people start to pay attention to the stabilities of the metal organic polymers. At present, people have synthesized a lot of metal organic polymers, but mostly organic frameworks would collapse without guest molecules, so they couldn't form permanent porosity. But there are some metal organic polymers with prefect thermal stability could gain the permanent porosity. But most of those metal organic polymers could collapse when they contact water, and even left them in air, so they couldn't exist in boiling water. For example MOF-5 has perfect thermal stability and higher surface area, and the study of it has been deeply. But MOF-5 could exist in vapor only less than 48 hours, and this limited the application of many character. Up to now, the reported microporous crystalline materials which could stability in boiling water is the zeolite-like frameworks ZIF-8. This material could stably exist in boiling water for 7 days, but at present metal organic polymers materials have been not so stable as it. we choose rare earth ion lanthanum as metal center and 8-hydroxyquinoline-5-sulfonic acid as organic ligand to obtained three novel no-interpenetrating three-dimensional open frameworks with honeycombed one-dimensional channels La₂(QS)₃(DMF)₃·3(H₂O) (1), La₂(QS)₃(H₂O)₃·3 (DMA) (2)å’ŒCe₂(QS)₃(DMF)₃ (3). We pay important attention to the thermal stability, hydrothermal stability, nitrogen adsorption property, hydrogen storage capability, methane adsorption property and fluorescence property of compound 1 and 2, and at the same time we importantly study the nitrogen adsorption property under different activation condition. Compound 1 and 2 could both be stable when the temperature is up to 350℃in air, but also they have perfect hydrothermal stability, they can keep stable in boiling water above one month, in water with the temperature of 130℃above twenty days, and in water with the temperature of 160℃above twenty days. It is most outstanding that these two compounds are hydrothermally ultra-stable compared to any other MOFs or ZIFs materials even all the porous materials. Nitrogen adsorption of compound 1 and 2 show the adsorption amount about 244 cm³ /g, 272 cm³ /g and with the Langmuir surface area of 1073 m²/g, 1197 m²/g. respectively.We choosing transition metals (Mo, Co, Ni, Mn) react with 8-hydroxyquinoline-5-sulfonic acid and gain five metal organic polymers under solvothermal condition. The reaction is between Mo and 8-hydroxyquinoline- 5-sulfonic acid to obtain the compound MoO₄C₁₈N₂H₁₄ (4)。The reactions between Co, Ni and 8-hydroxyquinoline-5-sulfonic acid obtain two compound 5 and 6 with extremely similar 2D layered structures. Co(QS)(H₂O)₂ (5) and Ni(QS)(H₂O)₂ (6) are the 3D supramolecular framework structure connected byÏ€-Ï€interactions and H-bond interactions. The reactions between Mn and 8-hydroxyquinoline-5-sulfonic acid obtain two 3D compounds Mn(C₂O₂H₆)SO₄ (7) and Mn(QS)(H₂O) (8) by altering different solvent. We pay important attention to the fluorescence spectra of compound 5, 6 and 8 and magnetic susceptibility properties of compound 5, 7 and 8. The isothermal of magnetic susceptibility properties of compound 7 and 8 suggest strong antiferromagnetic interactions in the range 4-300 K. The isothermal of magnetic susceptibility properties of compound 5 suggests strong antiferromagnetic interactions in the range 12-300 K, ferromagnetic interactions in the range 4-12K. A better insight into the structure of compound 8, we find it with rutile topological.At last we choose main group metal Ba and Mg react with 8-hydroxyquinoline-5-sulfonic acid and obtain two metal organic polymers. And Mg reacts with 5-sulfosiophthalic acid to obtain one tet-nuclear cluster. Ba reacts with 8-hydroxyquinoline-5-sulfonic acid in the solvent of DMF under solvothermal condition. In this reaction, DMF hydrolysis result reacts with two 8-hydroxyquinoline-5-sulfonic acids in situ to obtain a new ligand. This new ligand reacts with Ba to obtain a novel 3D compound.