A Study On Synthesis, Structures And Properties Of Transition Metal-5-sulfoisophthalate Complexes

The complexes based on organosulfonates are attracting more and more attentioncurrently because of their fascinating structures, interesting properties and potentialapplications in catalysis, gas storage, magnetism, ion conductivity, molecularrecognition and sensor devices, optics devices and so on, owing to the specialcoordination active sites, complicated coordination mode and the tend to formhydrogen bond of organosulfonates. The multifunctional5-sulfoisophalic acid （SIP）are chosen to react with Cd（Ⅱ）, Zn（Ⅱ） and Ag（I） of d10transition metal forconstructons of tansition metal-5-sulfoiphthalate complexes. Three parts of work inthe thesis have been carried on:1. Pyridine derivatives are chosen as auxiliary ligands and four new supermoleculecomplexes have been synthesized through hydrothermal reactions, namely,{[Cd（SIP）（2,2’-bpy）（H₂O）₂]₂[Cd（2,2’-bpy）（H₂O）₄].4H₂O}_n（1）、{[Cd（SIP）（Hbpe）].3H₂O}_n（2）、{[NaZn₂（SIP）₂(H_0.5bpp2（bpp）₂（H₂O）₂].8H₂O}_n（3）、{[Ag（HSIP）（4,4’-bpy）][Ag（4,4’-bpy）].2H₂O}_n（4），and structure analysis and characterization of thesecomplexes have been studied through X-ray diffraction technique, IR, TGA andspectrum technology, which have indicated that the four complexes all have the3Dframeworks packing with non-covalence supermolecule interactions: In Complex1,SIP coordinates with metal center in monodentate mode, together with hydrogenbonds and the Ï€-Ï€ stacking interactions between the auxiliary ligands2,2-bpy,3Dframework with the anion layers and cation layers alternately is packed. In Complex2,SIP connects four metal centers in hexdentate mode,and the3D porous framework isconstructed Ï€-Ï€ stacking interactions, with the cavity size of10.2×16.5A². InComplex3, SIP adopts the novel coordination mode μ₂-η²:η¹and μ₂-η⁰:η²toconnect metal centers, and3D nano-porous structure with the size of23.1×26.6A²cavities is formed by Ï€-Ï€ stacking interactions et al.. While in Complex4, SIP linksmetal centers in a monodentate mode and the3D framework has been facilitated byhydrogen bonds,Ï€-Ï€ stacking interactions and weak matal-metal bond interactions.The four complexes show good thermal stability and photoluminescence properties. 2. Two new supermolecule compounds have been assembled successfully undertemplate action of organophosphine [Ph₄P]+cation,{[（Ph₄P）（H₂SIP）].H₂O}_n（5） and{[Zn（SIP）（H₂O）Br][Ph₄P]₂.3H₂O}_n（6）. And it is shown that5is a salt-like3Dsupramolecular compound with packing layer structure, while6has the “sandwich”mode3D framework constructed by supermolecular interations such as coordinationbonds between SIP and metal centers, intermolecular hydrogen bonds, stackinginteractions and so on. And it is found that6has better thermal stability andphotoluminescence properties than5.3. The appropriate host in the complex {[Ag₃（SIP）（bpe）₃].10H₂O}_n（7） constructedby SIP, bpe and metal centers has been successfully induced and captured the objectswater and a novel water tape T5（0）A2has been formed.