Synthesis, Structure And Performances Of Coordination Polymers With N-, O-containing Or Chlorine Ligands

Crystal engineering is to study the behavior of molecular or chemical groups, the design and the control of crystal structure and properties, and prediction of crystal structure. To use energy and geometries of molecular interactions of different types, constructs the crystal of intended structure and properties in order to design the novel materials. The latest research fields of crystal engineering include inorganic-organic hybrid materials, micro porous materials, molecular magnets, coordination polymer and etc. By selecting the functional center metal ion and special organic ligands, directional design and synthesis of crystal materials can be realized in some extent, and at the same time, the chosen functional center metal ions and functional groups of organic ligands endow target crystal materials with optics, electrical, magnetic, separation and chiral catalysis properties, etc.. The explorations of structure and performance on these new systems can not only enrich the theoretical and experimental researches but also further expand the prospective applications for electron, optics, magnetism, chemical, and biological catalysis simulation and so on. In this paper, functional coordination polymers and inorganic-organic hybrid materials arise from hydrothermal condition.The paper is divided into five chapters. In the first chapter, we introduce the basic concepts, development process, the research domain and the latest research progress of coordination polymer, while the synthetic methods are depicted in detail. Under different reaction system, four types involved in 16 coordination polymers, which are structurally characterized by IR, XRD, elemental analysis, TGA and fluorescence etc., are obtained and the various factors of the synthesis are investigated. This gives rise to some information about the relationship of the structure and function.1. Five coordination polymers containing pyridine carboxylic acid polymer 1-5, [Pb(na)2]n,[Pb(in)2(H2O]n,Cu(in)2(H2O)4,[Pb(phen) 2 (in)]( NO3)·3H2O,Cd(in)2(H2O)4 (na= nicotinic acid, in=iso nicotinic acid). In compound 1, a PbO6N2 lead atom is 8-coordinated by six oxygen atoms and two nitrogen atoms displaying a distorted cubic geometry. The zigzag chain is formed by edge-sharing PbO6N2 cubic. Its three-dimensional structure is constructed by linking the chain of PbO6N2 polyhedra with nicotine acid molecules. Along (001) direction, four nicotinic acid molecules and four leads constitute the channel. In compounds 2, Pb atom coordinated with eight atoms forms two-capped triangle prism. The coordination atoms come from four different nicotinic acids and two water molecules. There are two different nicotinic coordination modes:μ2-?1: ?1: ?1 is denoted as L1,μ2- ?1: ?2 as L2. One oxygen atom of nicotinic acid and a water molecule bridge Pb respectively to form one-dimensional zigzag inorganic–Pb-O-Pb-O- skeleton. The adjacent chain is linked by different nicotinic acid (L1) to form three-dimensional network with square lattice in which L2 nicotinic group is trapped. The three-dimensional network shows typical diamond topology configuration, which comprise of 10 Pb atoms and six different nicotinic acid molecules. Compounds 3, 5 are the isomorphism coordination mononuclear compounds. The metal atoms in 3, 5 center the position of octahedron. The axis positions are occupied by two nitrogen atoms of isonicotinic, and the equator positions are occupied by four water molecules. A oxygen atom of Cu(in)2(H2O)4 unit and two water molecules H-bond four oxygen atoms of carboxyl to form 2D supramolecular layer. Then, the oxygen atoms on layers connect the oxygen atoms of nicotinic acid on the adjacent layer to constitute the 3d supramolecular network. In Compound 4, lead coordination geometry is typical hemi-direction in which all of the coordination bonds are concentrated in the hemispherical area, and other hemisphere has noticeably space. Free nitrate and three water molecules interact through the hydrogen bonding indicating a two-dimensional supramolecular anion layer, in which there is a large 20 member ring and small 20 member ring. The large ring is made up by 10 water molecules and six nitrate, and small ting by two water molecules and two nitrates. In every large ring, two [Pb(phen)2(in)]+ are filled as the guest.2, four coordination polymer 6-9 containing pyridine dicarboxylic acid ligands, Ni(3,5-pydc)(4H2O), PbCu(3,5-pydc)Cl, Pb(2,6-pydc)(pydc= pyridine dicarboxylic acid). In compound 7, the center lead atoms and four different pyridine dicarboxylic acids constitute hemidirected coordination model. Two carboxyl groups coordinated to the Pb atom by bidentate mode, and the other two carboxyl groups by monodentate mode. Cu cations locate at the bottom planar of tetrahedron, three atoms of which come from nitrogen atom of pyridine dicarboxylic acid and two chlorine atoms. The oxygen atom from another pyridine acid lies in vertex of tetrahedron. The adjacent leads are connected by doubleμ2 bridging oxygen and singleμ2 bridging oxygen to form 2D inorganic metal oxide frame. Six leads are connected by Pb-O-Pb to form Pb6 ring, which connects six adjacent Pb6 rings leading to the formation of two-dimensional inorganic oxygen skeleton. Pb6 connects two Pb6 ring by sharing-edge and four Pb6 ring by sharing-vertex. The two-dimensional inorganic metal layer is connected by the dicarboxylic acid pyridine to three-dimensional open frame. The two arrangements of A and B exist in two-dimensional metal oxide layer. According to ....ABAB.... arrangement, this kind of inorganic metal layer is connected to the three-dimensional network by pyridine dicarboxylic acid. If only considering inorganic skeleton, (CuCl)2 unit just locates in Pb6 ring. Compounds 8 and 9 are crystal polymorphism. Lead is connected by four different pyridine dicarboxylic acid to constitute hemidirected model. Every 2,6-pyridine dicarboxylic acid connected with four lead atoms forms the 2D two-dimensional layer. Six leads are connected by Pb -O- Pb to form Pb6 ring, which connect six Pb6 ring displaying forming two-dimensional inorganic oxygen skeleton.3. Five compounds containing organic and inorganic bridging ligands with 10-14, Pb(phen)(NO3)2, Pb(2,2-bpy)(NO3)Cl, Pb2.5(op)2bza, Cu2(4,4-bpy)Cl2, Cu(phen)(PMA) (op=phthalic acid, bza=benzoic acid). In compound 10, PbO8 shows geometry of two-capped triangle prism. Byπ-πstacking interaction and C-H…O hydrogen bond, a dimmer synthon are formed. Then, dimmer synthon form 1D chain byπ-πstacking interaction, which further form 2D layer by C-H…O hydrogen bond interaction. In compound 11, PbO8 shows geometry of two-capped triangle prism. Every nitrate links adjacent [Pb(bipy)(H2O)]2+ to 1D zigzag chain byμ2-?1:?1:?1 mode, which bridges by chorine to layer。The layer is stacked to 3D supermolecular network by strongπ-πinteraction。In compound 13, Cu atom locates the center of tetrahedron of three Cl- and one N of bipy. Every Cu links three Cl-, while every Cl- links three Cu to ladder chain. This ladder chain is connected to 2D layer by 4,4-bipy. In compound 14, CuⅡpolyhedron shows pyramid. Every PMA adoptsμ4 linkage, and while carboxyl group adoptsμ1-?1:?1 andμ1-?1:?0 to link four Cu to 1D double-strand。In structure, four double-strands and hydrogen of water construct 1D supermolecular channel, of which size is 7.93 ?×12.11?. In channel, adjacent phen molecules form 1Dπ-πstacking interaction.