Syntheses And Characterizations Of Sulfo-carboxylic Acid Organic Ligands And Their Metal-organic Compounds

Metal-organic compounds as an important class of solid-state materials have potential applications in gas-storage, photoelectron materials, magnetic materials and catalytic properties. The research of metal-organic compounds has emerged as a hot chemical topic in organic chemistry, inorganic chemistry, solid state chemistry and materials chemistry. Metal-organic materials bear the advantages of the organic ligands and inorganic ions. The organic component possesses the tailorability, while the inorganic metal ion possesses diverse electronic, magnetic and optical properties.This work presented in this dissertation deals with the synthesis and characterization of two sulfo-carboxylic acid organic ligands, namely 5-sulfoisophthalic acid (H₃SIP) and 4,8-disulfonaphthalene-2,6-dicarboxylic acid organic ligands(H₄DSNDA), and their metal-organic compounds. Firstly, we described the synthesis of the two organic ligands through sulfonations. Then twelve metal-organic compounds were obtained from transition metal ions or lanthanide ions with the H₃SIP or H₄DSNDA organic ligands. (a) Hydrothermal reactions of transition metals ions with 5-sulfoisophthalic acid ligands, afforded three new compounds, namely [Zn(μ₂-OH)(SIP)(DPP)(H₂O)]_n (1), {[Zn₃(μ₂-OH₂)₂(SIP)₂(phen)₃(H₂O)₃]- (H₂O)₅}_n (2) and Cu4(μ₃-OH)₂(SIP)₂(imz)₂](H₂0)₂} (3). (b) Hydrothermal reactions of lanthanides metal ions with 4,8-disulfonaphthalene-2,6-dicarboxylic acid, produced other nine new novel compounds, {[Pr4(μ₃-OH)4(DSNDA)₂(H₂O)₁₂](H₂O)₁₂}_n (4), [Ln((H-DSNDA)_0.5(DSNDA)_0.5(H₂O)₅]_n (Ln = La (5), Nd (6), Gd (7), Eu (8),Dy (9) and Sm(10)), [(H-DPP)₂Eu₂(DSNDA)₂(H₂O)8]_n (11) and {[Er(H-DSNDA)(H₂O)4] (H₂O)}_n (12). The two organic ligands have been charcterized by NMR and IR spectra. The general characterizations such as single-crystal X-ray diffraction and IR spectra are carried out on all these metal-organic compounds. Magnetic susceptibility measurements, thermal-gravity analyses and fluorescent spectra are performed on part of these compounds. The topological structures of part of compounds are studied.Five chapters are covered in this dissertation: The mechanisms of the sulfonation, the background, and brief introduction of the latest research progress on the metal-organic compounds with sulfonate-carboxylate ligands are reviewed in Chapter 1. Chapter 2 describes the self-assembly of the twelve metal-organic compounds with H₃SIP or H₄DSNDA organic ligands. Structural characterization of the two organic ligands also provided in Chapter 2. In chapter 3, crystal structures of the twelve compounds are described. Compound [Zn(μ₂-OH)(SIP)(DPP)(H₂O)]_n (1) has a three-dimensional (3D) network where the zinc ions are bridged by 5-SIP3- and DPP ligands. The 3D structure contains left- and right-handed Zn-SIP helical chains with equivalent numbers. Compound {[Zn₃(μ₂-OH₂)₂(SIP)₂(phen)3(H₂O)3](H₂O)₅}_n (2) has an one-dimensional (1D) chain structure containing two kinds of basic structure units. Compound Cu4(μ₃-OH)₂(SIP)₂(imz)₂](H₂0)₂} (3) is a 3D structure based on tetranuclear [Cu4(μ₃-OH)₂]⁶⁺ unit and has a rutile topology. Compound {[Pr₄(μ₃-OH)₄(DSNDA)₂(H₂O)₁₂](H₂O)₁₂}_n (4) is a 3D structure based on tetranuclear [Pr₄(μ₃-OH)₄]8+ unit. Each [Pr₄(μ₃-OH)₄]8+ unit is linked by eigth DSNDA4- ligands to form a 3D structure with 1D rhombic channels. Compounds 5– 10, ([Ln((H-DSNDA)_0.5(DSNDA)_0.5(H₂O)₅]_n (Ln = La (5), Nd (6), Gd (7), Eu (8), Dy(9) and Sm(10)) are isomorphous and have wavy two-dimensional (2D) structures. [(H-DPP)₂Eu₂(DSNDA)₂(H₂O)₈]_n (11) has a 2D layered structure with square grids, charged with the protoned H-DPP ligands. {[Er(H-DSNDA)(H₂O)₄](H₂O)}_n (12) is a 2D layered structure. In Chapter 4, the physical properties, such as photoluminescence and magnetic properties, of these compounds are investigated. A brief conclusion and an outlook on this work are presented in the last chapter.