Design, Synthesis And Properties Of New Coordination Polymers Constructed By Polycarboxylic Acid

In recent years, the design and construction of new functional coordination polymers cause more attention due to their novel topological structures and potential applications in the fields of optical, electrical, magnetism, adsorption and catalytic.Especially the design and construction of coordination polymer based on organic polycarboxylic acid, which not only can provide multiple potential donor atoms, but also show rich coordination modes. So the coordination polymer formed by organic polycarboxylic acid have varied structures and wide range of uses. This dissertation is aimed to synthesize luminescent coordination polymers by the reaction of d10 metal ions(Zn2+,Cd2+,Ag+)and rare earth ions(Pr3+?Tb3+)with three different types of organic polycarboxylic acids. Three series, 14 d10 transition /lanthanide coordination polymers are designed and constructed. All metal complexes are characterized by X-ray single crystal diffraction, IR spectra and luminescence analyses. This dissertation includes the following four chapters:(1) The Chapter 1: Preface, introduce the coordination chemistry, synthetic method of coordination polymers, and the research progress of coordination polymer based on organic polycarboxylic acid.(2) The Chapter 2: Six novel metal complex 1-6 based on 5-(3',4'-dicarboxylphen oxy) isophalic acid(H4dppa) and Cd2+, Zn2+ ion have been synthesized successfully.[Cd(H2dppa)(bpy)]n(1), [Cd2(dppa)(dye)]n·nH2O(2), [Zn2(dppa)(Phen)2·H2O]n(3), [Cd4(dppa)2(H2O)9]n·nH2O(4), [Zn2(dppa)(bpy)2(H2O)]n·nH2O(5), [Cd2(dppa)(Dpe)2(H2 O)]n.nH2O(6). In complex 1 and 3, each ligand ion connects three CdII ion by five teeth chelating bridging model. Complex 2 shows 2D network structure built from tetranuclear tetranuclear cadmium clusters cross-linked by(dppa)4- ligands via ten teeth chelatingbridging coordination mode. Complex 4 is a 2D network structure,(dppa)4- ligand took eight teeth chelating bridging coordination model. In complex 5, each(dppa)4- ligand shows seven teeth chelating bridging coordination model; Complex 6 is a 3D network structure formed by binuclear cadmium cluster bridging ligand, each ligand took nine teeth chelating bridging coordination model. In addition, element analysis, IR, the thermal stablities and photoluminescence properties of 1-6 were also studied.(3) The Chapter 3: We have synthesized four novel lanthanide metal complex 7-10 based on 5-(3',4'- bis(tetrazol-5'-yl)phenoxy) isophthalic acid and Pr3+, Tb3+ ion. [Pr(btpa)(H2O)(OH)]n?nbpy(7), [Tb(btpa)(H2O)(OH)]n?nbpy(8), [Pr(btpa)(phen)2(OH)]n?n H2O(9), [Tb(btpa)(phen)2(OH)]n? nH2O(10). In complexes 7-10,(btpa)2- ligand shows two different coordination models: In 7-8,(btpa)2- ligand took six teeth chelating bridging coordination model; In 9-10,(btpa)2- ligand possess a 1D chain structure.(btpa)2- ligand join two metal ions with chelating bidentate /chelating bidentate model. Besides, we also studied the elemental analyses, IR and the fluorescence spectrum of them.(4) The Chapter 4: Four d10 transition metal coordination polymers 11-14 based on benzophenone-2,4'-2 formic acid(H2bdam) and Zn2+, Cd2+ and Ag+ ion have been hydrothermal synthesized. [Cd(bdam)(phen)2]n(11), [Cd(bdam)(bpy)]n·nH2O(12), [Zn(bdam)(bpy)]n·nH2O(13), [Ag4(bdam)2(dpe)]n(14). In 11,(bdam)2- ligand took monodentate bridging/bidentate chelating model with two Cd II ions to form 1D square wave chain structure; 12 shows a 1D ring chain structure containing 28 atom ring. 13 is a 1D right-handed helical chain formed. 14 possesses a 2D network structure based on octanuclear silver units.(bdam)2- ions took seven bridge coordination model. In addition,we also studied the elemental analyses, IR and the fluorescence spectrum of them.