Synthesis, Structures And Properties Of Coordination Polymers Based On Phenanthroline Derivatives

Coordination polymers, also known as the Metal-Organic Frameworks（MOFs）,are attracting increasing attention owing to their applications in the field of newmultifunctional materials by academia over the last decade. MOFs are mainlyconstructed by the metal center ions and organic ligands through coordination bondsconnection, having one-dimensional, two-dimensional or three-dimensional infiniteperiodic network structure or zero-dimensional molecular cage. Such compounds notonly have fascinating structural topologies, but also have potential applications incatalysts, molecular recognetion, gas adsorption, optics, electrics and magnetism.We take a series of phenanthroline derivatives as organic ligands, according to theprinciples of crystal engineering, to build new metal-organic coordination polymers withspecial structures and properties under hydrothermal conditions. The structures andsynthesis conditions of the synthesized compounds are described in detail on thisthesis. All of our works have accumulated a wealth of experimental data for the designedand synthesized of such coordination polymers, which are based on H2PPDA.Furthermore, they also provide some experimental materials to the design and synthesisof metal organic coordination polymers.The first chapter briefly describes the research and development of coordination polymers; summarizes the synthesis methods of coordination polymers; the influencingfactors in constructing coordination polymers; coordination polymers in situ reactions（in situ ligand reaction and in situ metal reaction）; the development of coordinationpolymers research based on （2,3-f）-Pyrazino（1,10） phenanthroline-2,3-dicarboxylicacid（H2PPDA）; the purpose, significance and major research results of our work. Wealso have introduced the main experimental reagents and characterization of testmethods used in this paper.In chapter Ⅱ, we choose transition-metal （Zn） and （2,3-f）-Pyrazino（1,10）phenanthroline-2,3-dicarboxylic acid through in situ ligand reaction to produce azero-dimensional compound [Zn2（phen）₂（ida）₂]·3H2O （1）[phen=1,10-phenanthro--line, H2ida=iminodiacetic acid] under hydrothermal conditions. In compound1, thetwo nitrogen atoms of phen adopt a typical bidentate chelating coordination mode.Each H2ida ligand was fully deprotonated into ida2-, linking Zn centers through theη1:η1:η2:μ2coordination mode, with one bridging carbonyl oxygen connecting thetwo metal Zn atoms in the same plane to form a parallelogram with another bridgingcarbonyl oxygen. Moreover, three organic crystals （C₁6H₇N₄O₄）Na·2H₂O （2）,C₁6H₈N₄O₄（3）,（C₁6H₈N₄O₄）·H₂O （4） have been produced and their structures arecharacterized.In chapter Ⅲ, we report two transition metal Cd coordination polymers basedon H2PPDA,[Cd（Dpq）Cl₂]（5） and [Cd（Dpq）Cl₂]（6）. Both compounds are isomersof each other. The ligand H2PPDA were changed into dipyrido[3,2-d:2’,3’-f]quinoxaline（Dpq）. In compound5composed of one-dimensional chains, everycenter Cd atom exhibits Mitsubishi column geometry and all the bridged chlorineatoms （μ-2） are in the same plane, the existing way of the chlorine atoms has notbeen reported. The π-π conjugate intention exists between the adjacent chains.Different from compoud5, the metal center of compound6shows irregularoctahedral configuration. Fused heterocyclic π-π interaction between adjacentone-dimensional infinite chains comes from the relative Dpq molecules, which is anunusual, almost completely overlapping aromatic system of accumulation. Compound6has a high thermal stability and good fluorescence characteristics.