Synthesis,Structures And Properties Of Metal-organic Frameworks Based On N/O-containing Ligands

This dissertation consists of three parts:Firstly, we used1,2-phenylenediacetic acid and1,2,4,5-benzenetetracarboxylic acid ligands synthesized three coordination complexes which have novel structures and properties by hydrothermal and solvothermal reactions. Secondly, three coordination complexes with novel structures and properties were synthesized by hydrothermal reactions with3-(4-chlorophenyl) glutaric acid ligand; Thirdly, we obtained five coordination complexes with N/O-containing ligands by solvothermal and hydrothermal reactions.1. Synthesis, Structures and Properties of Metal-organic Frameworks Based on1,2-Phenylenediacetic acid (PDDA) and1,2,4,5-BenzenetetracarboxyIic acid (BTCA) LigandsTwo new lanthanon complexes, namely,{[Nd(PDAA)1.5(H2O)]}n(1),{[La(PDAA)1.5(H2O)]·H2O}n(2), and one transitional metal complex {[Cu2(BTCA)·H2O]}n(3) were synthesized under solvothermal and hydrothermal reactions based on ligands1,2-phenylenediacetic acid and1,2,4,5-benzenetetracarboxylic acid, the fluorescence properties of1and2were researched. Complexes1and2have similar3D supermolecule structures, for PDAA, there are two kinds of coordinated modes in complex2. In complex3, BTCA coordinated with Cu in two kinds of modes obtained3D supramolecular structures with channels.2. Synthesis, Structures and Properties of Metal-organic Frameworks Based on3-(4-Chlorophenyl) glutaric acid (CPGA) LigandWe have synthesized three new transitional metals coordination complexes, namely,{[Zn(CPGA)2(H2O)2]}n(4),{[Cd3(CPGA)3]}n(5) and {[Zn(CPGA)(DPPP)·H2O]}n(6) under hydrothermal methods based on ligands3-(4-Chlorophenyl) glutaric acid and1,3-Bis(4-pyridyl) propane (DPPP), the fluorescence properties of4-6were researched. Complex4is zero-dimensional structure. Hydrogen bonds connecting zero-dimensional structures obtained2D planar structures. There are2D wave-like sheets in complex5, which obtained by CPGA and Cd(II). In complex6, CPGA, DPPP and Zn(Ⅱ) were connected to form a2D layer, two2D layers connected through hydrogen bonds forming2D double layers, and2D double layers were not joined further.3. Synthesis, Structures and Properties of Metal-organic Frameworks Based on N/O-containing ligandsFive coordination complexes which have novel structures and properties, namely,[Ni(bipy)(Metha)2]n·nH2O(7),[Co(bipy)(Metha)2]n·nH2O(8),(Cu2(TPOM)(GA)2}n(9),{[Fe(phen)3]-2(O-BDC)H3O+-3H2O}n(10),[Cd(6-GA)2]n(11)(biby=4,4’-bipyridine, Metha=methane acid, GA=glutaric acid, phen=1,10-phenanthroline monohydrate, HO-BDC=5-Hydroxyisophthalic acid, TPOM=tetrakis(4-pyridyloxymethylene)methane,6-GA=6-Aminonicotinic acid) were synthesized based on N/O-containing ligands by hydrothermal and solvothermal reactions. Complexes7and8are isomorphic, methane acid and4,4’-bipyridine are connected with Ni and Co to form a3D supramolecular structure. There are two types of coordination modes with Cu(Ⅱ) in complex9, square and octahedral Cu centers are coordinated with the TPOM ligands forming2-double interlocked3D network structure. In compound10, Fe(Ⅲ) joined with three phen ligands forming zero-dimensional structure, zero-dimensional structures were joined with the existence of π-π interaction between the phen ligands forming one-dimensional chains. O-BDC anions did not participate in the coordination. One-dimensional chains filled in the channels which obtained by O-BDC anions and water molecules. In complex11,6-Aminonicotinic acid coordinated with Cd (Ⅱ) ions, forming a one-dimensional chiral chain structure, this is the first coorination complex with6-Aminonicotinic acid.