Syntheses, Structures And Properties Of Several Novel Metal-organic Coordination Polymers

The rational design and assembly of the metal-organic frameworks（MOFs） hasbeen flourishing in recent years and received remarkable attention not only due to theirintriguing frameworks but also because of their interesting properties and potentialapplications in optical, electronic, and magnetism, gas storage, ion exchange, molecularrecognization, enantioselective separation and catalysis. The purpose of this paper is toutilize the principles of crystal-engineering based on organic ligands and metal centerswith specific coordination geometries to design and synthesize the metal-organicframeworks. The main contents in the thesis were summarized as follows:In the paper, we have adopted two carboxylate ligands:3,3’,4,4’-oxydiphthalicacid （H₄ODPA） and4-carboxyl-4’-hydroxy azobenzene （H₂L）, The crystal structuresand properties of these complexes have also been investigated.In the first chapter, it has been introduced the basic concept, research backgroundand progress in coordination chemistry. The synthesis methods and influencing factorsof metal-organic coordination polymers and their applications have also beendemonstrated.In the second chapter, an achiral semi-flexible tetra-carboxylate ligand,3,3’,4,4’-oxydiphthalic acid （H4ODPA）, was synthesized according to the literaturemethod. Using H4ODPA and auxiliary ligands, we have been synthesized four metal（II）complexes formulated as Ni₂（ODPA）（4,4’-bpy）₂（H₂O）4·H₂O （bpy=bipyridine）（1）,Cu8（H₂ODPA）8（₂,₂’-bpy）8（H₂O）4·7H₂O （₂）, Co3（ODPA）₂（₂,₂’-bpy）3（H₂O）₁₀·₂H₂O （3）and Zn₂（ODPA）（L1）₂·3H₂O （HL1=gatifloxacin）（4）. Complex1shows a uninodal3-connected₂D layer with {8₂.10} topology, Packing of the₂D layer leads to chiralarchitecture in complex1; Complexes₂and3are tetranuclear Cu（II） and mononuclearCo（II） complexes, respectively; Complex4shows a chain-like structure. Complex1shows strong CD signal, and complexes₂-4are achiral. The supramolecular packings incomplex1account for the chiral features of the structure. The four complexes showdifferent UV-vis absorption and photoluminescence properties as well as differentthermal stability.In the third chapter, an azobenzene derivative,4-carboxyl-4’-hydroxy azobenzene（H₂L） was prepared according to the literature method. An organic ligand and its Cu（II）complex formulated as (C₁₃H₁₀N₂O₃)·5H₂O （H₂L·5H₂O）（5） and Cu（HL）₂（phen）（6） have been synthesized. In the two compounds, H₂L and HL exhibit a trans-conformation. Complex6shows a mononuclear Cu（II） structure with the hydroxylgroup of HL uncoordinated. Complex6is assembled into a three dimensional （3D）supramolecular architecture by hydrogen bonds and π-π stacking interactions. H₂L andcompound6can detect NO₂via reversible and irreversible color changes. Themechanism for the color changes is investigated.