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

The metal-organic coordination polymers （MOPs） with variety of structures andgreat potential applications in the fiels such as sorption, separation, heterogenouscatalysis, photoelectricity and chemosensor is one hot topic in inorganic chemistry,physical chemistry and material chemistry. The choices of organic ligands are importantfor the structures and properties of the MOPs, and the carboxylic acid and sulfonic acidorgnic ligands have attracted much attention for the rational combinations of carboxylicacid with strong coordination abilities and sulfonic acid with weak coordination abilitesmay result in a large number of functional MOPs. So, in the thesis, we choose5-Sulfo-1,2,4-benzenetricarboxylic acid as organic linker to synthesize the MOPs withvarious metal ions, and hope to obtain some functional materials.Eight Metal-organic coordination compounds have been obtained, and their structures, fluorescence, and magnetic properties have also been characterized andinvestigated by single-crystal X-ray diffraction, element analysis, IR spectroscopy,thermal-gravity analyses, magnetic susceptibility measurements, and fluorescent spectra. In coumpound [Cd₂（SBTC）（DPP）_1.5]_n（1）, the SBTC^4-ligand links Cd（II） ions to form a two-dimental layer along ab plane, and the2D layer is further linkerd by DPP ligand to give a three-dimentional structure. In the photoluminescence spectra of compouns1, the fluorescence emission at442nm can be attributed to intraligand emission of DPP. Compound [Cd₄（SBTC）₂（2,2′-bpy）₆（H₂O）₄]（2,2′-bpy）（2） is a isolated tetranuclear molecule, and the tetranuclear molecule furtherextends to one-dimentional chain through the hydron bonds between the coordinated H2O molecule, carboxylic oxygen atom and sulfonic oxygen atom. In heterometallic compound {[K₂Cd（SBTC）（H₂O）₅]（H₂O）}_n（3）, the Cd（II） and K（I） ions are linked by oxygen atoms of carboxylic acid and sulfonic acid group of SBTC4-ligand, and water molecule to form a two-dimentional heterometallic oxo-layer， which further linked by benzene ring of SBTC^4-ligand and water molecule to produce a3D structure. Compound [K₂（H₂-SBTC）（H₂O）₂]_n（4） is also a3D structure and its fluorescence at460nm can be ascribed to the intraligand emission ofH₄SBTC ligand. Compound [Yb（SBTC）（ox）（H₂O）₅]_n（5） features a2D layer, which produce a3D structure through hydrogen bonds. The magnetic data of5shows that the magnetic exchange actions between Yb（III） ions belong to antiferrimagnetism. Interestingly, in compound {[Zn₂（SSCC）（DPP）₂]（H₂O）₂}_n（6）,[Mn（SSCC）_0.5（2,2′-bpy）（H₂O）₂]_n（7） and [Ni（2,2′-bpy）（H₂O）₄]（SSCC）_0.5（8）, the2,5-disulfo-1,3-Benzenedicarboxylic anion (SBTC^4-) is in situ synthesized from the reaction of H4SBTC ligand and Yb（III）, Zn（II）, and Mn（III） respectively.{[Zn₂（SSCC）（DPP）₂]（H₂O）₂}_n（6） is a3D structure, which can produce white fluorescence. Compound[Mn（SSCC）_0.5（2,2′-bpy）（H₂O）₂]_n（7） features a1D chain, and the1D chain furthergave a3D supermolecular structure through the hydrogen bonds and π-π packing between the2,2′-bpy ligands. Compound [Ni（2,2′-bpy）（H₂O）₄]（SSCC）_0.5（8） isa mononuclear structure, in which the SSCC4–ligand does not participate in coordination but act as counter ions.Four chapters are presented in this dissertation: the chapter I introduces the research progresses and potential applications of the metal-organic coordination polymers; In Chapter II, five compounds,([Cd₂（SBTC）（DPP）_1.5]_n（1）,[Cd₂（SBTC）（2,2′-bpy）₃（H₂O）₂]（2,2′-bpy）_0.5（2）,{[K₂Cd（SBTC）（H₂O）₅]（H₂O）}_n（3）,[K₂（H₂-SBTC）（H₂O）₂]_n（4） and [Yb（SBTC）（ox）（H₂O）₅]_n（5）, constructed from5-Sulfo-1,2,4-benzenetricarboxylic acid, have been introduced including the structure, fluorescence and magnetic properties of these compounds; Chapter III contains three metal-organic coordination polymers,{[Zn₂（SSCC）（DPP）₂]（H₂O）₂}_n（6）,[Mn（SSCC）_0.5（2,2-bp′y）（H₂O）₂]_n（7）, and [Ni（2,2′-bpy）（H₂O）₄]（SSCC）_0.5（8）. Interestingly, the2,5-disulfo-1,3-Benzenedicarboxylic anion (SSCC^4-) is formed in situ by the reactionof5-Sulfo-1,2,4-benzenetricarboxylic acid and the metal ions. The structures ofall three compounds have been characterized by single-crystal X-ray diffraction, element analysis, and IR spectroscopy. The magnetic properties of compound7ha ve also been investigated; A brief conclusion and an outlook on this work are presentedin the last chapter.