Synthesis Of Coordination Polymers By Nitrogen Heterocyclic Carboxylic Acid

As an ideal ligand for constructing metal organic coordination polymers,nitrogen heterocyclic carboxylic acid possesses outstanding skeletal structure,strong coordination ability, extensive coordination modes and multiple coordination sites.Combined with the advantages of N-donor and carboxylate ligands, the coordination polymers of nitrogen heterocyclic carboxylic acid are advanced with novel structure,strong stability, rich features and functionality.In this thesis, three different kinds of nitrogen heterocyclic carboxylic acid ligands have been used to react with meatl ions: 2,2’-bipyridine-4,4’-dicarboxylic acid(ligand1), 4’-(3,5-di(4-carbonylphenyl)phenyl)-2,3’:6’3”-terpyridine(ligand2), and the mixed ligands including 2,5-pyridinedicarboxylic acid(pydc),terephthalic acid(bdc) and1,10-Phenanthroline hydrate(phen). Ten new metal-organic frameworks formed by the above ligands through hydrothermal reaction have been obtained:{[La(C12H6N2O4)(C12H7N2O4)(DMF)2]·2H2O}n(1),{[Eu(C12H6N2O4)(C12H7N2O4)(DMF)]·DMF·2H2O}n(2),{[Dy(C12H6N2O4)(DMF)2(NO3)]·2H2O}n(3), {[Tb(C12H6N2O4)(DMF)2(NO3)]·2H2O}n(4),{[Ni(C35H21N3O4)]·DMF·H2O}n(5), {[Cd(C35H21N3O4)]·DMF·H2O}n(6),{[Mn(C35H21N3O4)]·DMF·H2O}n(7), [Pr(pydc)(bdc)0.5(H2O)]n(8),{[Sm(Pydc)(bdc)0.5(Phen)]·H2O}n(9), {[Nd(pydc)(bdc)0.5(phen)]·H2O}n(10).The composition, crystal structures, morphologies, sizes and properties of the complexes have been studied by X-ray single crystal diffraction, Fourier transform infrared spectrum, Elemental analysis, Thermal analysis and Fluorescence testing.The main contents as follows:1. The analysis shows that the complex(1) belongs to monoclinic, space group C2/c.Formed the distorted square antiprism geometry with La3+ as the central ion. Adjacent La3+ions are connected through ligand1 to form the 2D layered structure, which are further linked to three-dimensional structure.2. The analysis reveals that the complex(2) belongs to monoclinic, space group P21/c.Formed the double-capped triangular prism geometry with seven oxygen atoms and one nitrogen atom.The secondary building units of complex(2) are combined by carbonyl-oxygen to have cage structure and extends to three-dimensional structure.3. Complex(3) and(4) are allomerism, both belong to triclinic, space group P-1and C2/c. Formed dodecahedron geometry and linked to three-dimensional structure though carbonyl-oxygen of ligand1.4. Complex(5) belongs to monoclinic, space group P21. Formed the octahedron geometry with Ni2+ as the central ion. Adjacent Ni2+ ions are connected through carbonyl-oxygen of mono or bi-dentate-fashion to form the 2D layered structure.Complex(6) and(7) are allomerism, both belong to monoclinic, space group P12(1)/n1, trigonal bipyramid structure. Compared to complex(5), carbonyl-oxygen of ligand2 only has mono dentate-fashion to connect central ions to form a one dimensional chain.5. Complex(8) belongs to monoclinic, space group P21/c. Nine donor atoms formed tri-capped triangle prism with Pr3+as the central ion. The complex formed a 2D layered structure by connection of 2,5-pyridinedicarboxylic acid(pydc), which were further linked to three-dimensional structure through auxiliary ligand terephthalic acid(bdc).6. Complex(9) and(10) are allomerism, both belong to triclinic, space group P-1.Nine donor atoms formed tri-capped triangle prism. Carbonyl-oxygen of2,5-pyridinedicarboxylic acid(pydc) connected central ions to form a one dimensional chain, which were further linked to three-dimensional structure through auxiliary ligand terephthalic acid(bdc).