Metal Sulfonate Synthesis, Structure And Characterization

Polymers with novel structures which are constructed by the self-assembly of multifunctional ligands and metal ions have attracted much attention for their potential use in conductivity, separation, adsorption and catalyst. Among these functional polymers, many are synthesized by the N-containing ligands, carboxylates and phosphate ligands. However, the coordination chemistry of the sulfonate group has been relatively less studied. In this paper, 4-aminobenzenesulfonic acid, 2-aminopyridine-5-sulfonic acid, and 3-aldehyde-4-hydroxybenzenesulfonate sodium are selected as sulfonate ligands, pyridine, 1,10-phenanthroline, 4,4'-bipyridie, and hexamethylenetetramine as secondary ligands to study the coordination modes of the sulfonate. 19 new compounds were synthesized and studied. 7 crystal structures of the compounds were determined.The paper is divided into five chapters.In chapter 1, the research and the development of the metal sulfonate compound were summarized.In chapter 2, the instrustments, the reagents and the test methods are listed.In chapter 3, 9 new compounds were synthesized by the reaction of metal ions with 4-aminobenzenesufonic acid , pyridine and other secondary ligands. They were charactered by IR and elemental analysis. Compounds 1 and 9 were also studied by thermal analysis and single-crystal structure analysis. In compound 1, the sulfonate anion adoptsη~1 coordination mode, while in compound 9, it exists only as counteranion.In chapter 4, 2-aminopyridine-5-sulfonic acid was synthesized and studied. 5 new compounds were obtained and charactered by IR and Elemental analysis. The structures of the compounds 13 to 15 were studied. The results showed that in compounds 13 and 15, the sulfonate anion adoptsη~2 andη~1 coordination modes respectively, while in compound 14, it is uncoordinated. The open-ring of the hexamethylenetetramine was first observed in compounds 13 and 15.In chapter 5, 3-aldehyde-4-hydroxybenzenesulfonate sodium was synthesized and studied together with 1,10-phenanthroline as secondary ligand. 4 new compounds were obtained and charactered by IR and Elemental analysis. The structures of cmpounds 16 and 19 were determined. The sulfonate anion both adoptsη~1 coordination modes. The photoluminescent of compounds 16 and 19 were also studied, together with the thermogravimetric analysis of compound 19.