Synthese, Structures And Property Study Of Coordination Polymer Based On Pydiyl Carboxylate Acid And Its Derivatives

As a newly-identified functional molecule-based materials, metal-organic coordination polymer (MOCP) has been a focus of material chemistry due to their flexible tailoring structures, charming topological networks as well as their fascinating potential applications in functional solid materials ions exchange, adsorption, catalysis, and the development of optical, electronic, and magnetic devices.Coordination polymers may easily be affected by various factors, such as the environment of the metals, the structure of the organic-ligands, the appropriate reaction conditions, which may make a great change on the formation of the advanced structures. At the present time the synthesized coordination polymers have took on abundant structure topologies, for instance the one-dimensional linear chain, Zigzag chain, helical chain, rotaxane type, tow-dimensional honeycomb type, stick and wall type, graphite type, square lattice type, three-dimensional diamond type and primitive cubic types and so on.Organic-ligands with the luxuriant structures play an important role in the construction of the coordination polymers, e.g. carboxylate type, pyridine type,-CN type and so on. At present, chemists have realized the construction of coordination polymers using two different kinds of organic-ligands with one metal ion or one organic-ligand assemblied with two different metals. Furthermore, the strategies for the synthesis of the materials are various, such as solvent volatilization, room temperature diffusion, hydrothermal solvent thermal, pillared method and so on.The aim of this thesis is the synthesis of new coordination compounds on the basis of pyridyl acid and pyridyl acid N-oxide ligands (pyridine-3,5-dicarboxylic acid, isonicotinic acid, nicotinic acid, isonicotinic acid N-oxide, nicotinic acid N-oxide, and 2,2'-bipyridyl-3,3'-dicarboxyl-1,1'-dioxide) and metal ions. The study on synthetic conditions and rules for these new compounds, topological analyses, and the exploration of relationships between structures and properties for these new compounds are also carried out.Twenty-two new coordination compounds have been synthesized on the basis of hydrothermal technique and/or water solution synthesis methods and structurally characterized by elemental analyses, IR, XRPD, TG and single crystal X-ray diffractions. The thermal stabilities, magnetic properties and fluorescent activity of these compounds have been studied.1. Six new compounds on the basis of pyridine-3,5-dicarboxylate (PDB) and coligands of different configurations have been synthesized through hydrothermally and traditional methods and structurally characterized including three 1-D chain, 2-D layered structures constructed by transition metals{[Ni(PDB)(H2O)]n 1, [Co2(PDB)2(bpy)2]?(H2O) 3, [Co2(PDB)2(phen)]n 4}, and three 2-D, 3-D frameworks constructed by main group metals {[Pb(PDB)(H2O)]?(H2O) 2, [Pb(INA)2]?H2O 5, [Pb(NA)2]n 6}.Compounds 1-4 are only constructed by PDB and divalent metals salts. Because PDB ligand has diversity coordination modes and chelating ligands are introduced, compounds 1-4 exhibit different structural characters. Compounds 5 and 6 are two novel structures constructed by lead and isonicotinic acid or nicotinic acid ligand. The studied result of two structures shows that the coordination strategies and coordination geometries of metal ion PbII effects the structures of final products. In addition, the luminescent properties of compound 2 and magnetic property of compound 4 are also investigated.2. Three 3-D frameworks with 1-D channels {[Pb(INO)2]2·7H2O 7, [Pb(INO)2]·nH2O 8, [Pb4(OH)4(INO)4]·nH2O 9} and three 3-D supramolecular compounds {[Pb(INO)2]·3H2O 10, [Pb(INO)2·NO3·H2O]n 11, Na1.5[Pb2(INO)5]·0.5NO3 12} have been synthesized hydrothermal technique and/or water solution synthesis methods on basis of isonicotinic acid N-oxide and lead(II), and the influence of the pH value of system on the final network has been studied.Compounds 7-9 have three-dimensional structures that are only constructed by HINO and lead, and 1-D channels were found in three structure. Compound 7 features a most remarkable and unique 3D framework with two distinct kinds of channels showing different sizes and shapes, which are occupied by two kinds of water clusters, respectively, according to the size and shape of the channels. The structure of 9 consists of [Pb4(OH)4]4+ cluster inorganic building blocks, which connect withμ4-INO ligands through oxygen atoms from N-oxide moieties and carboxylate groups of INO to form 8.7×8.7 ?2 rhombic channels running along the c-axis. Compounds 10-12 have three-dimensional supramoleculr structures that are constructed by HINO and lead. Compound 10, consisting of 1D infinite chain, is 3D supramolecular framework with 1D rectangle channel, in which free water molecules locate. The structure of 11 consists of 1D chains built by two parallel L3 ligands bridging to a pair of rhombic-planar [Pb2O2] units, which is further extended into a 2D supramolecular layer via interlayerπ-πinteraction. In compound 12, the self-assembly based on 2D motifs with side arms leads to the formation of a new type of polythreaded network, which contains 1D channels located guests molecules along the b-axis.3. Six new compounds with different dimensionalities have been hydrothermally synthesized on the basis of nicotinic acid N-oxide (NNO) and metal ions lead(II): [Pb3(NNO)4·(NO3)2]n 13, [Pb(NNO)2]n 14, [Pb(NNO)2]2·nH2O 15, [Pb(NNO)(FA)0.5]n 16, [Pb(NNO)(SA)0.5]n 17, [Pb2(NNO)(BTC)]n 18.Compound 13 possesses of two kinds of Pb-O chains, which are bridged by NNO ligand to give a 2D network. Compounds 14 and 15 are isomer exclude lattice water molecules. Compound 14 is a 2D layer structure and in the intralayer regions there exists parallel left- and right-handed helical chains. Compounds 16-17 are isostructural and their frameworks constructed by NNO and carboxylate ligand exhibit an interesting one-dimensional zig-zag chain. Compound 18 is show 3-D structures when ligand H3BTC is introduced.4. Four metal-organic frameworks have been hydrothermally synthesized on the basis of 2,2'-bipyridyl-3,3'-dicarboxyl-1,1'-dioxide (H2BDCD) ligand and 4,4'-bpy ligand and transion metal ions {[Zn0.5(BDCD)0.5·H2O]n 19, [Zn(BDCD)(bpy)0.5]n 20, [Cd3(BDCD)3(bpy)3]n 21, [Ni2(BDCD)2(bpy)2]2n 22}.Compound 19 only constructed by H2BDCD ligand and zinc(II) shows an interesting one-dimensional zig-zag chain. Compound 20 shows 3-D supramolecular networks and exhibits an unprecedented (44·62)(44·66) topology when chelating ligands are introduced, whereas compounds 21-22 exhibit 2-D frameworks. The fluorescent studies on the compounds based on d10 metals are discussed.