Syntheses, Structures And Properties Of Coordination Polymers Based On V-like Pyridyl-bis-amides Ligands

In this thesis, N,N’-bis(pyridine-3-yl)pyridine-2,6-dicarboxamide(L1), N,N’-bis(pyridine-3-yl)pyridine-3,5-dicarboxamide(L2) and N,N′-bis(pyridine-3-yl)-5-methylisophthalic dicarboxamide(L3) were selected as the main ligands and dicarboxylates with different spacers [2, 5-pyridinedicarboxylic acid(H2pdda), 2-carboxymethylsulfanyl nicotinic acid(H2cmsn), oxalic acid(H2ox), trans-1,4-cyclohexanedicarboxylic acid(H2chda), 5-methylisophthalic acid(H2mip), 4,4′-oxybis(benzoic acid)(H2oba), 5-hydroxyisophthalic acid(H2hip), 2,5-thiophenedicarboxylic acid(H2tpd) and 1,3-benzenedicarboxylic acid(H2BDC)] have been used as the auxiliary ligands to react with transition metal atoms under hydrothermal conditions. Thirty-five new complexes have been synthesized and characterized by IR, TG, PXRD and single-crystal X-ray diffraction. The fluorescent property and photocatalytic activity of some polymers have been studied.1. Using V-like tri-pyridyl-bis-amide(L1 and L2) as main ligands and different dicarboxylates as auxiliary ligands, twenty-seven one-dimensional(1D)–three dimensional(3D) transition metals complexes with different structural features have been hydrothermally synthesized and structurally characterized. The influence of the tri-pyridyl-bis-amide ligands with different spacers, the dicarboxylates and the central metals on the sructures of complexes has been investigated.[Co(L1)2(Hpdda)2]n(1){[Co(L1)(oba)(H2O)]·2H2O}n(2){[Co(L1)(cmsn)]·3H2O}n(3){[Ni(L1)(mip)(H2O)]·3H2O}n(4){[Ni(L1)(hip)(H2O)3]·3H2O}n(5){[Ni4(L1)4(oba)4(H2O)2]·10H2O}n(6){[Zn(L1)(mip)]·H2O}n(7){[Zn2(L1)2(hip)2]·H2O}n(8){[Zn(L1)(oba)]·H2O}n(9){[Zn(L1)(chda)]·H2O}n(10){[Cd2(L1)(mip)2(H2O)]·2H2O}n(11){[Cd(L1)(hip)]·4H2O}n(12){[Cd(L1)(oba)]·H2O}n(13){[Cd3(L1)(chda)3]·4H2O}n(14[Zn(L2)(mip)]n(15){[Zn(L2)(hip)(H2O)]·3H2O}n(16)[Zn(L2)(oba)]n(17){[Cd(L2)(hip)]·3H2O}n(18){[Cd(L2)(oba)]·H2O}n(19)[Cd(L2)(chda)]n(20){[Ni(L2)(mip)(H2O)] ·2H2O}n(21){[Ni2(L2)2(hip)2(H2O)2] ·4H2O}n(22){[Ni(L2)(oba)(H2O)2]H2O}n(23){[Co(L2)(ox)]·3H2O}n(24)[Co2(L2)(chda)2]n(25){[Co(L2)(mip)(H2O)]H2O}n(26)[Co(L2)(oba)]n(27)Single crystal X-ray diffraction analysis reveals that complex 1 is a discrete 0D complex. Complexes 2, 4, 6, 9, 16, 21 and 22 exhibit similar one dimensional tubular structures constructed from 28-membered [M-L]2 loops(M = Co Ni,and Zn; L = L1 and L2) with different sizes and linear [M-X]n chains(M = Co Ni,and Zn; X = mip, hip and oba). In 3, the CoII ions are linked by L1 ligands to generate 1D wave-like chain, which is further connected by the cmsn anions to form a 2D network. In complex 5, L1 ligands connect the adjacent NiII ions constructing two types of 1D chains: left-, right-helical chain [Ni-L1]n, which are further extended into a 2D supramolecular double layer by hydrogen bonding interactions. Complex 7 features a two-dimensional(2D) network, which consists of a linear [Zn-mip]n chain and [Zn-L1]n left-, right-handed helixes. Complex 8 is a 2-fold interpenetrating 2D�'2D network. Complex 10 is a 2D layer containing [Zn-chda]n right-handed helixs and Zn2(L1)2 loops. Complex 11 features a 1D belt structure based on Cd4(COO)4 subunits. Complex 12 exhibits a 2D network constructed from [Cd-hip]n ladder-like chains and Cd2(L1)2 loops. Complex 13 and 19 shows a 1D double chain structure containing [Cd-oba]n zigzag chain and [Cd-L1]n meso-right-handed helix. Complex 14 exhibits a 2D network based on 2D [Cd-chda] layer and 1D [Cd-L1]n meso-helical chain. Complex 15 is a 2D layer containing [Zn-mip]n linear chain and [Zn-L2]n meso-helical chain. Complex 17 exhibits a 2D grid network containing 1D [Zn-oba]n and [Zn-L2]n chains. Complex 18 shows a 2D layer based on [Cd2(hip)2]n double chain and [Cd-L2]n chain. Complex 20 is a 3, 5-connected 3D framework with the Schl?fli symbol of(42.65.83)(42.6), which is constructed from [Cd-L2]n channel-like chains and chda linkers. In complex 23, the L2 ligands adopting μ3-bridging mode connect adjacent NiII ions to form a 1D channel-like structure. In 24, the oxalate anions display μ2-bridging mode connecting the adjacent 1D [Co-L2]n zigzag chains to afford a 2D layer. In 25, the chda anions take the μ4-bridging mode connecting the neighboring four CoII ions to construct a [Co-chda]2n 1D double chain, which contains the Co2(CO2)4 paddle-wheel subunit. These double chains are further linked by L2 ligands to furnish a 2D layer. In 26–27, CoII ions are linked by L2 ligands to give rise to a 1D left-, righthelical chain [Co–L2]n, respectively. These helical chains are further linked by μ2-bridging mip and oba anions to furnish a 2D network, respectively.The structural diversities of the title complexes indicate that the metal ions, N-donor ligands and dicarboxylate with different spacers play great effect in the assembly of target complexes. Moreover, the fluorescent selectivity of the complexes 9′, 12′, 13′ and 19′ for certain organic solvents make them promising candidates as fluorescent sensor materials. The photocatalytic activity and selectivity of the complexes 7-20 prove that they may be good and stable photocatalysts for degradation of organic dyes.2. Eight new CdII/ZnII coordination polymers tuned by an unprecedented “V”-type bi-pyridyl-bis-amide ligand(L3) and different dicarboxylates have been hydrothermally synthesized and structurally characterized. The structural diversity of the title complexes indicates that the dicarboxylates and the central metals play important roles in tuning the structures of the target complexes.{[Cd(L3)(tpd)(H2O)]·H2O}n(28){[Cd(L3)(BDC)(H2O)]·H2O}n(29){[Cd(L3)(mip)(H2O)]·H2O}n(30){[Cd(L3)(hip)(H2O)]·H2O}n(31){[Zn(L3)(tpd)(H2O)]·H2O}n(32){[Zn(L3)(BDC)(H2O)]·H2O}n(33){[Zn(L3)(mip)(H2O)]·H2O}n(34){[Zn(L3)(hip)]·2H2O}n(35)In complexes 28, 30 and 31-34, the L3 ligands adopt μ2–bridging mode bridge adjacent CdII/ZnII ions to give rise 1D left-, right-handed helixes. In complex 29, the L3 ligands connect adjacent CdII to form a 1D right-handed helix. In complex 35, the L3 ligands link adjacent ZnII to obtain a 1D wave-like chain. The adjacent 1D chains [Zn-L3]n are further linked by hip anions with monodentate-chelating or monodentate-bridging mode to furnish a 2D layer structure.The central metals with different radii influence the coordination modes of dicarboxylates. The dicarboxylates with carboxyl groups in meta-position show great effect on the formation of 2D networks for the title compounds. The photocatalytic activity and selectivity of the complexes 28–35 prove that they may be good and stable photocatalysts for degradation of organic dyes.