Syntheses, Crystal Structures And Properties Of Metal-organic Coordination Polymers Constructed From6-sulfonyl-1,4-naphthalenedicarboxylic Acid Ligand

Metal-organic compounds have emerged as an interesting class of hybridmaterials. The intense interest in these materials is driven by their intrinsicarchitectural beauty and aesthetically pleasing structures, as well as potentialapplications in many diverse areas, including gas storage, catalysis, molecularmagnets, photoluminescence, nonlinear optics, ferroelectrics, and drug delivery. Theinorganic metal ion confer useful magnetic or optical properties, and thermal stability,while the organic component offers a potential for structural diversification, so thecombination of the characteristics of the organic and inorganic components offer avast area of complex and multifunctional materials of metal-organic compounds.This work presented in this dissertation deals with the synthesis and structuralcharacterization （such as IR spectrum and nuclear magnetic resonance spectrum） of anovel6-sulfonyl-1,4-naphthalenedicarboxylic acid organic ligand （H₃sndc） withsulfonate and carboxylate groups. The fluorescent emission of the organic ligand hasbeen investigated. Ten metal-organic coordination polymers based on the6-sulfonyl-1,4-naphthalenedicarboxylate ligand have been obtained. Compounds withstructural types ranging from1D chains to2D layers to3D networks have beensynthesized under various conditions. All compounds have been structurallycharacterized by single-crystal X-ray diffraction and infrared spectra. The thermalstability of these compounds has also investigated. The fluorescencent properties ofsome of the compounds have been studied in detail.Four chapters are covered in this dissertation:Chapter1: The brief introduction of the latest research progress on thecoordination chemistry and the metal-organic compounds with carboxylate ligandsand sulfonate-carboxylate ligands are reviewed in.Chapter2: The synthesis and structural characterizations of four lanthanidecoordination polymers based on the6-sulfonyl-1,4-naphthalenedicarboxylic acidligand is provided in this chapter. The synthesis, crystal structures, and properties ofthe four isomorphous {[Ln（sndc）（DMF）（H₂O）]（DMF）（H₂O）_1.5}n（Ln=Eu（1），Sm（2），Pr（3），Nd（4）） compounds are described in this chapter. In {[Ln（sndc）（DMF）（H₂O）]（DMF）（H₂O）_1.5}n（Ln=Eu（1），Sm（2），Pr（3），Nd（4）） compounds, the sndc3-ligand linksLn3-ions to form two-dimensional layers. The guest DMF and water molecules filled the space between the two-dimensional layers and hydrogen bonded to the maintwo-dimensional layers.Chapter3: Reactions of transition metal ions and6-sulfonyl-1,4-naphthalenedicarboxylic acid ligand lead to six coordination polymers. Theirsynthesis, crystal structures, and properties are presented in this chapter. The generalcharacterizations such as single-crystal X-ray diffraction and IR spectra wereperformed on these metal-organic compounds. Compound {[Pb₃（sndc）₂]（H₂O）₂}n（5）has a three-dimensional structure where the sndc3-ligand links Pb（II） ions intothree-dimensional structure. Compound {[Pb₃（sndc）₂]（H₂O）₂}n（5） exhitbits aligand-centred emission. Compound [Bi₂O₂（H-sndc）（H₂O）]n（6） contains atetranuclear [Bi4（μ2-O）2（μ3-O）2] unit where four Bi（III） ions are bridged by fouroxygen anions. The tetranuclear [Bi4（μ2-O）2（μ3-O）2] units are linked by the H-sndc2-ligands to form a one-dimensional chain. Compounds [Cd（H-sndc）（phen）（H₂O）]n（7）,{[Mn（H-sndc）（phen）（H₂O）₂]}n（8） and {[Mn（H-sndc）（H-4,4′-bpy）（H₂O）₃]（ClO₄）（H₂O）₂}n（9） feature one-dimensional chain structures fromed from the organicligands and metal ions. Compound {[Ag（4,4′-bpy）]（H₂-sndc）（H₂O）₄}n（10） has atwo-dimensional layer structure wherein the4,4′-bpy ligand links Ag（I） ions to form aone-dimensional chain, which is further linked by the Ag···Ag interactions to give atwo-dimensional layer. The H-sndc2-anions and water molecules act as geustmolecules fills the space between the layers.Chapter4: A brief conclusion and an outlook on this work are presented in thelast chapter.