Mao Le

pH, solvent and metal ion induced octamolybdate-based metal–organic complexes decorated with a pyridyl-carboxylate ligand containing an amide group

Three octamolybdate-based metal–organic complexes constructed from a pyridyl-carboxylate ligand containing an amide group, 3-(2-pyridinecarboxylic acid)amido pyridine (HPCAP), namely, H2{[Cu3(PCAP)4(H2O)2](β-Mo8O26)}·10H2O (1), H{[Cu(PCAP)(H2O)](β-Mo8O26)0.5} (2) and H2[Co(H2O)6][Co2(PCAP)4(γ-Mo8O26)(H2O)2]·10H2O (3), have been successfully synthesized under hydrothermal or solvothermal (methanol–water mixed solvent) conditions. Single-crystal X-ray analyses reveal that compound 1 is a 2D layer based on infinite 1D [Cu3(PCAP)4]n2n+ chains and bidentate β-Mo8O264− anions. In compound 2, 1D “thin centipede” [Cu2(PCAP)2]n2n+ chains were connected by tetradentate β-Mo8O264− anions through the Cu–O bond to form a 2D network. In compound 3, γ-Mo8O264− anions were connected by adjacent [Co2(PCAP)4(H2O)2] moieties through Co–O and Mo–N bonds forming an uncommon 1D “fat centipede” chain. The adjacent chains were further extended to a 2D supramolecular network through hydrogen bonding interactions. The title compounds represent the first examples of introducing a pyridyl-carboxylate ligand containing an amide group into the POM system. The pH value, solvent and metal ions play key roles in the construction of the final architectures and show a great influence on the structural diversities of the title compounds. The electrochemical properties of compound 1 and the photocatalysis properties of the title compounds have been reported.

Assembly, structures, photophysical properties and photocatalytic activities of a series of coordination polymers constructed from semi-rigid bis-pyridyl-bis-amide and benzenetricarboxylic acid

A series of new metal(II)–organic coordination polymers, namely [Co(3-DPNA)(1,3,5-HBTC)]·2H2O (1), [Ni(3-DPNA)1.5(1,3,5-HBTC)(H2O)2] (2), [Cu(3-DPNA)(1,3,5-HBTC)]·H2O (3), [Zn(3-DPNA)(1,3,5-HBTC)]·2H2O (4), [Cd(3-DPNA)(1,3,5-HBTC)(H2O)]·2H2O (5), [Co(4-DPNA)(1,3,5-HBTC)]·4H2O (6), [Ni(4-DPNA)(1,3,5-BTC)2/3] (7), [Cu(4-DPNA)(1,3,5-BTC)2/3] (8), [Zn(4-HDPNA)(1,3,5-BTC)] (9), [Cd(4-DPNA)(1,3,5-BTC)1/3Cl] (10), have been purposefully synthesized under hydrothermal conditions [N1,N4-di(pyridin-3-yl)naphthalene-1,4-dicarboxamide (3-DPNA) and N1,N4-di(pyridin-4-yl)naphthalene-1,4-dicarboxamide (4-DPNA), 1,3,5-H3BTC = 1,3,5-benzenetricarboxylic acid]. Complexes 1 and 4 exhibit similar 1D belt-like chains constructed from 1D left- and right-hand [Co-(3-DPNA)]n helical chains and [Co-(1,3,5-HBTC)]n linear chains. Complex 2 furnishes a 1D [Ni-(3-DPNA)1.5]n “loop + line” chain with 1,3,5-HBTC anions hanging on both sides. Complex 3 features a 2D sql network based on [Cu-(3-DPNA)]nmeso-helical chains and [Cu-(1,3,5-HBTC)]n linear chains. Complex 5 shows a 1D ladder-like chain constructed from [Cd-1,3,5-HBTC]n linear chains and [Cd2(3-DPNA)2] loops. Complex 6 displays a 2D double sheet containing (H2O)8 clusters. Complexes 7 and 8 possess similar 3D (3,4)-connected frameworks with the (63)2(64·8·10)3 topology containing a dodecagon-shape cavity and a hexagonal cavity, respectively. Complex 9 shows a 2D network, in which one pyridine nitrogen atom of 4-DPNA was protonated. Complex 10 is a 3D (3,5)-connected framework with (3·44·63·82)3(63) topology. All the 1D chains and 2D networks are further extended into 2D supramolecular sheets or 3D supramolecular frameworks through hydrogen-bonding interactions. The influence of metal(II) ions and N-donor ligands on the structures of the title compounds was investigated. The results suggest that the central metals with various coordination nature and the semi-rigid bis-pyridyl-bis-amide ligands with different coordination sites show a great effect on the structures of the title compounds. In addition, the fluorescence sensing properties of 4, 5, 9, and 10 and the photocatalytic activities of complexes 1–10 have been investigated in detail, and the results show that 5 possesses good fluorescence selectivity for different solvent molecules.

A series of bis(pyridyl)-bis(amide)-modulated metal-1,2-phenylenediacetate coordination polymers: construction and selective dye adsorption

Five new coordination polymers (CPs), namely, [Cu(3-bpcb)(1,2-pda)]·2H2O (1), [Cu(4-bpah)(1,2-pda)(H2O)]·H2O (2), [Ni2(4-bpah)2(1,2-pda)2(μ2-H2O)] (3), [Cu3(4-bpfp)(1,2-pda)2(μ3-OH)2] (4), [Co(4-bpfp)0.5(1,2-pda)(H2O)] (5), were prepared by hydrothermal reactions of metal(II) chloride with 1,2-H2pda (H2pda = 1,2-phenylenediacetic acid) in the presence of different bis(pyridyl)-bis(amide) ligands (3-bpcb = N,N′-bis(3-pyridinecarboxamide)-1,4-benzene; 4-bpah = N,N′-bis(4-pyridinecarboxamide)-1,2-cyclohexane; and 4-bpfp = N,N′-bis(4-pyridylformyl)piperazine) and structurally characterized by single crystal X-ray diffraction, infrared spectroscopy (IR), elemental analysis, powder X-ray diffraction (PXRD) and thermogravimetric analysis (TGA). Complexes 1–3 show three different 2D layers with diverse (42·67·8)(42·6), (44·62) and (42·6)(42·67·8) topological structures, respectively. Complex 4 exhibits a 3D polymeric framework, which presents a novel (3,4,8)-connected topology with the Schlafli symbol (3·4·5)2(32·42·52·614·74·83·9)(32·63·7). Complex 5 displays a 3D network with 3,4-connected (42·63·8)(42·6) topology. The diverse arrangements of these complexes show the remarkable sensitivity of the metal(II)–H2pda system to the different bis(pyridyl)-bis(amide) ligands. In addition, the electrochemical properties of complexes 3–5 and the dye adsorption properties of the title complexes are also discussed.

Three 2 D copper(II)/cadmium(II) coordination polymers based on semi-rigid/flexible bis-pyridyl-bis-amide ligands and 5-aminoisophthalate: Syntheses, structures and properties

AbstractThree new transition metal coordination polymers [Cu(3-bpcb)0.5(5-AIP)] ⋅2H2O (1), [Cd(3-bpc b)0.5(5-AIP)(H2O)] ⋅H2O (2) and [Cd(3-bpsa)0.5(5-AIP)(H2O)] ⋅2H2O (3) have been hydrothermally synthesized by self-assembly of 5-aminoisophthalic acid (5-H2AIP), semi-rigid or flexible bis-pyridyl-bis-amide ligands [3-bpcb = N N ′-bis(3-pyridinecarboxamide)-1,4-benzene, 3-bpsa = N,N ′-bis(3-pyridyl)succinamide], and copper chloride or cadmium nitrate. X-ray diffraction analysis reveals that compounds 1 and 2 possess similar 2 D double-layered structures with (3,4)-connected (63)(65⋅8) topology, while compound 3 displays a 2 D layer with {62.10}{6} topology. The adjacent layers of 1–3 are finally extended into 3 D supramolecular frameworks by hydrogen bonding interactions. The bis-pyridyl-bis-amide ligands with different flexibilities play an important role in the construction of final topological structures for the title compounds. Further, the electrochemical behavior of the compound 1 and the fluorescent and photocatalytic properties of compounds 1–3 have been investigated. Graphical AbstractThree new copper(II)/cadmium(II) coordination polymers have been hydrothermally synthesized by self-assembly of 5-H2AIP, semi-rigid or flexible bis-pyridyl-bis-amide ligands and copper chloride or cadmium nitrate. The electrochemical behavior, the fluorescent and photocatalytic properties of the compounds have been investigated.

A Cd-Coordination Polymer Based on a Bis-pyridyl-bis-amide Ligand: Synthesis, Structure and Its Application in Removal Organic Dyes

A cadmium(II) coordination polymer, namely, [Cd2(3-bpcb)(1,2-pda)2(H2O)2] (1), was prepared by hydrothermal reaction of cadmium(II) chloride with 1,2-H2pda (H2pda = 1,2-phenylenediacetic acid) and a bis-pyridyl-bis-amide ligand (3-bpcb = N,N′-bis(3-pyridinecarboxamide)-1,4-benzene). Complex 1 was structurally characterized by single crystal X-ray diffraction, which shows a 2D layer structure with (42·6)(42·63·8) topology. Complex 1 was further characterized by elemental analysis, infrared spectroscopy (IR) and thermogravimetric analysis (TGA). The application in removal organic dyes of complex 1 has been investigated.

Four Cu(II)/Co(II) coordination polymers based on N,N′-di(3-pyridyl)sebacicdiamide: influence of different carboxylate ancillary ligands on structures and properties

Abstract Four Cu(II)/Co(II) coordination polymers, [Cu(L)(BDC)(H2O)]·3H2O (1), [Cu(L)(DNBA)2] (2), [Co(L)2(DNBA)2] (3), and [Co(L)(NIPH)(H2O)]·H2O (4) (H2BDC = 1,4-benzenedicarboxylic acid, HDNBA = 3,5-dinitrobenzoic acid, H2NIPH = 5-nitroisophthalic acid, L = N,N′-di(3-pyridyl)sebacicdiamide), have been synthesized under hydrothermal conditions. The structures of 1–4 have been determined by single-crystal X-ray diffraction analyses and 1–4 were further characterized by infrared spectroscopy and thermogravimetric analyses. Complex 1 is a 2-D polymeric layer with a 4-connected sql topology. Complex 2 displays a 1-D zigzag chain. Complex 3 possesses a 1-D double-chain structure. Complex 4 exhibits a ribbon chain based on the 1-D [Co–L]nmeso-helical chain. Adjacent layers for 1 and adjacent chains for 2–4 are further linked by hydrogen bonding or π–π stacking interactions to form 3-D supramolecular networks. The differences of carboxylates and metal ions show significant effect on the ultimate architectures of the four complexes. Thermal stabilities, fluorescent properties and photocatalytic activities of 1–4 were also studied.

Effect of Reaction Conditions on the Assembly, Structures and Fluorescent Sensing Behaviors of Cd（II） Metal-organic Complexes

Three Cd(II) metal-organic complexes, namely [Cd(phen)2Cl2](1), [Cd(phen)Cl2](2) and [Cd(phen)(cam)]· H2O(3)(phen=1,10-phenanthroline, H2cam=camphoric acid), were hydrothermally synthesized using Cd2+, phen and H2cam as raw materials under different conditions of pH values, reaction temperatures or reactant ratios. The prepared complexes were structurally characterized by means of single-crystal X-ray diffraction, and the results show that complex 1 is a 2D supramolecular complex, which consists of [Cd(phen)2Cl2] mononuclear subunits, while complex 2 shows a 1D chain structure, in which Cd(II) ions are connected by chloride(Cl–) bridges, with phen hanging on both sides of the chain. No cam anions have been observed in the structures of complexes 1 and 2. In complex 3, cam connects Cd(II) ions to construct a 2D network, in which phen acts as terminal ligands. The adjacent 1D chains for complex 2 and the adjacent 2D layers for complex 3 are further linked by hydrogen bonding interactions or π-π intermolecular interactions to form 3D supramolecular networks, respectively. The effects of reaction conditions on the assembly and structures of the complexes have been discussed. The fluorescent and photocatalytic properties of complexes 1―3 and the fluorescent sensing behaviors of complexes 2 and 3 have also been investigated.

Flexible bis(pyridyl-tetrazole) ligand-induced ring-containing metal–organic coordination polymers: synthesis, structures, and properties

Abstract Three coordination polymers (CPs), [Co(3-bptzp)(BDC)] (1), [Zn(3-bptzp)(BDC)] (2), and [Cd(3-bptzp)(BDC)] (3) (3-bptzp = 1,4-bis(5-(3-pyridyl)tetrazolyl)propane, H2BDC = 1,3-benzenedicarboxylic acid), were synthesized under hydrothermal conditions. The CPs were structurally characterized by single-crystal X-ray diffraction, infrared spectroscopy (IR), elemental analyses, and powder X-ray diffraction (PXRD). Complexes 1–3 represent the first examples of CPs based on the flexible bis(pyridyl-tetrazole) 3-bptzp. Structure analyses reveal that 1–3 are 1-D ring-containing polymeric chains. For 2 and 3, adjacent 1-D chains are extended to 2-D supramolecular networks by hydrogen bonding. Dye adsorption properties of 1–3, electrochemical properties of 1, and fluorescent-sensing behaviors of 2 and 3 have also been investigated.

Assembly and Selective Photocatalysis of Two Multifunctional Copper(II) Complexes Derived From a Bis-Pyridyl-Bis-Amide and Two Dicarboxylates

Two multifunctional metal-organic coordination polymers, namely [Cu(4-bpah)(2,6-PDA)] (1) and [Cu(4-bpah)(3-NIP)]·H2O (2), where 4-bpah = N, N′-bis(4-pyridinecarboxamide)-1,2-cyclohexane, 2,6-H2PDA = pyridine-2,6-dicarboxylic acid, 3-H2NIP = 3-nitrophalic acid, have been hydrothermally synthesized and structurally characterized by IR, TG, and single-crystal X-ray diffraction analyses. Complex 1 is a 1D infinite helix chain structure. Complex 2 possesses a 2D polymeric layer containing two kinds of meso-helical chains: [Cu-4-bpah]n and [Cu-3-NIP]n. The adjacent 1D chains for 1 or the adjacent 2D layers for 2 are further linked by hydrogen bonding interactions to form 2D or 3D supramolecular networks, respectively. The fluorescent, electrochemical and photocatalytic properties of complexes 1–2 have also been investigated.