| Aromatic multiphenyl carboxylate ligands are liable to construct various dimentional coordination polymers with novel structures, due to their abundant coordination modes, their strong chelating and bridging ability with metal ions, as well as their roles acted as donors or receptors of hydrogen bonds; One the other hand,mutiphenyl carboxylic ligands display robust structures with large delocalized πelectron system, can be used to prepare metal-aromatic mutiphenyl carboxylate coordination polymers with potential applications in magnetism, catalysis, luminescent materials, gas storage or separation, drug delivery, and mimicing of biological enzyme.In the thesis, through the selection of robust aromatic biphenyl/terphenyl tetracarboxylic ligands to react with various metal ions, eight metal-aromatic biphenyl/terphenyl tetracarboxylate coordination polymers were constructed. Meanwhile, the various reaction factors of synthesizing coordination polymers were invesitigated, such as the ratios of reactants, pH values of solution, temperature, polarity of solution, and anions.The thermal stability, luminescent properties and biological applications of targeted products were also explored, the detailed content is arranged as follows:(1)Five metal-aromatic mutiphenyl carboxylate coordination polymers based on3,3’,5,5’-biphenyl tetracarboxylate ligands were constructed under various conditions,such as Cu2(BPTC)(Bipy)2(H2O)(H2O)2(DMF)3(1); Zn2(BPTC)(DMF)2(H2O)·DMF·2H2O(2); Co2(BPTC)(DMF)2(H2O)·(DMF)(H2O)3(3); Co2(BPTC)(DMF)2·2H2O(4); Ni(BPTC)·solvent(5); and a byproduct Ni(bipy)(HCOO)2(6). The components, structures, and the properties of all compounds were systematically characterized. 1 is a framework with two-dimensional wave layer structure, 3 is a 3-pe riodic frameworks with PtS type topologies constructed from Co2(COO)4(H2O)(DMF)2units and BPTC; 1 displayed a strong blue and purple fluorescent emission band centered at 424 nm, 2 displayed a strong fluorescent emission band centered at 532 nm;3 is stable in large temperature range(200-423℃); we have also tried to explore the role in nonenzymatic glucose sensor such as complex 3 and 5, cyclic voltammogramsanalysis reveal that the modified electrode 3/Nafion/GCE and 5/Nafion /GCE can have electrochemical response to the small molecule organic compounds such as glucose, and3/Nafion/GCE is stable in contrast; load and release of the anti-cancer drugs 5 fluorouracil were also investigated for 5.(2)Two metal-aromatic mutiphenyl carboxylate coordination polymers based on3,3’,5,5’-terphenyl tetracarboxylate ligands were constructed under various conditions,such as Zn(TPTC)0.5(H2O)·4DMF(7) and(Me2NH2)Nd2(TPTC)2(DMF)(H2O)8.5H2O(8). Single-crystal X-ray diffractions reveal that 7 is a three-dimensional frameworks with NbO type topologies which is formed by TPTC4- bridging {Zn2(O2CR)4}paddle-wheel units, with double-hexagonal channels along [001] direction. 8 is a three-dimensional net framework constructed from two bridging mode of ligands. The components, structures, and the properties of all compounds were systematically characterized. Cyclic voltammograms analysis reveal that the modified electrode8/Nafion/GCE can separate instantly.This dissertation explores the synthesis of complexes based on different length aromatic muti-carboxylic acid and the structural analysis, studies the thermal stability,fluorescence property, electrochemical performance, and absorbability, try to get the the relationship between the property and structure or the strcture and construction units,provide the reference for the future design of supramolecular materials with specific function. |
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