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1.
Four new Cu(II) complexes [Cu(pzda)(2,2′-bpy)(H2O)] · 2.5H2O (1), [Cu(pzda)(phen)(H2O)] · H2O (2), [Cu(pzda)(4,4′-bpy)] · H2O (3) and [Cu(pzda)(bpe)0.5(H2O)] (4) were synthesized by hydrothermal reactions of copper salt (acetate or sulphate) with pyrazine-2,6-dicarboxylic acid (H2pzda), and 2,2′-bipyridine (2,2′-bpy), 1,10-phenanthroline (phen), 4,4′-bipyridine (4,4′-bpy) or 1,2-bis(4-pyridyl)-ethane (bpe), respectively. For 1 and 2, they are both monomeric entities which are further assembled into 3D supramolecular networks by hydrogen bonds and π-π stacking interactions. Complex 3 has a 2D metal-organic framework which is connected into 3D supramolecular network by hydrogen bonds. However, for 4, the bpe ligand bridges two Cu(II) ions into binuclear unit, and then the binuclear molecules are assembled into 3D supramolecular network by hydrogen bonds between the coordination water molecule and the carboxylate oxygen atoms. The thermal decomposition mechanism of complexes 1 and 2 cooperated with powder XRD at different temperatures is discussed. The results reveal that once liberation of water molecules takes place the supramolecular network of 1 and 2 collapses.  相似文献   

2.
Complexes 1 and 2, formulated {[Co2(4,4′-bpy)2 · 8H2O] · (CCA)2 · 4H2O}n (1) and {[Co(TMG)(4,4′-bpy)(H2O)2] · 3H2O}n (2) (H2CCA = 2-carboxylatocinnamate, H2TMG = 3,3-tetramethyleneglutate, 4,4′-bpy = 4,4′-bpyridine) have been synthesized by the reaction of cobalt (II), 4,4′-bpy and carboxylate ligands, in which 2D metal-water layers and 1D metal-water chains have been observed, respectively. In the metal-water clusters, the water molecules are trapped by the cooperative association of coordination interactions as well as hydrogen bonds.  相似文献   

3.
Hydrothermal reaction of the carboxylate-based ligands with metal salts (or oxide) and 4,4′-bipyridine as a second linker, afforded three new coordination polymers, namely, [Co(PCPA)2(4,4′-bpy)]n (1) with 2-D rectangle grids, Cu(PCPA)2(4,4′-bpy)]n (2) with a linear chain, [Ag(PCPA)(PCPAH)(4,4′-bpy) · H2O]n (3) with 1-D molecular ladder (4,4′-bpy = 4,4′-bipyridine; PCPA = p-chlorophenoxyacetate; PCPAH = p-chlorophenoxyacetic acid). It is noticeable that compound 3 is also a supramolecular framework built by coordination bonds, weak interactions between Ag ions, π-π stacking interactions and hydrogen-bonded interactions. The three compounds with different structure motifs have been characterized by elemental analyses, IR spectra, ultraviolet-visible diffuse reflection integral spectra, fluorescent spectra and single crystal X-ray diffraction analysis. Furthermore, the bonding properties of compound 3 were investigated in terms of the absorption spectrum, as well as the calculated band structures and density of states.  相似文献   

4.
Three new organic-inorganic hybrid materials with 4,4′-bipy ligands and copper cations as linkers, [CuII(H2O)(4,4′-bipy)2][CuII(H2O)(4,4′-bpy)2]2H[CuIIP8Mo12O62H12] · 5H2O (1), [CuI(4,4′-bipy)][CuII(4,4′-bipy)]2 (BW12O40) · (4,4′-bipy) · 2H2O (2) and [CuI (4,4′-bipy)]3 (PMo12O40) · (pip) · 2H2O (3) (pip = piperazine; 4,4′-bipy = 4,4′-bipyridine), have been hydrothermally synthesized. The single X-ray structural analysis reveals that the structure of 1 is constructed from [Cu(H2O)(4,4′-bipy)2] complexes into a novel, three-dimensional supermolecular network with 1-D channels in which Cu[P4Mo6]2 dimer clusters reside. To the best of our knowledge, compound 1 is the first complex in which the [P4Mo6] clusters have been used as a non-coordinating anionic template for the construction of a novel, three-dimensional supermolecular network. Compound 2 is constructed from the six-supported [BW12O40]5− polyoxoanions and [CuI(4,4′-bipy)] and [CuII(4,4′-bipy)] groups into a novel, 3-D network. Compound 3 exhibits unusual 3-D supramolecular frameworks, which are constructed from tetrasupporting [PMo12O40]3− clusters and [CuI (4,4′-bipy)n] coordination polymer chains. The electrochemical properties of 2 and 3 have been investigated in detail.  相似文献   

5.
Four coordination compounds of tetrazolate-5-carboxylate (tzc) with cobalt(II), [Co2(tzc)2(H2O)6]·2H2O (1), [Co2(tzc)2(phen)2(H2O)2]·2H2O (2), [Co2(tzc)2(2,2′-bpy)2(H2O)2]·H2O (3), and [Co(tzc)(4,4′-bpy)] (4), where phen = 1,10-phenanthroline, 2,2′-bpy = 2,2′-bipyridyl, and 4,4′-bpy = 4,4′-bipyridyl, have been synthesized by the hydrothermal methods involving the in situ generation of the ligand from sodium ethyl tetrazolate-5-carboxylate. Compounds 1, 2 and 3 all contain dinuclear molecules in which metal ions are linked by the double N-N bridges from two tzc ligands in the μ2-N1,O1:N2 mode, and the dinuclear molecules are associated into 3D architecture through extensive hydrogen bonding and π-π stacking interactions in various fashions. Compound 4 exhibits a two-dimensional layer structure in which Co(tzc) chains with μ3-N1,O1:O1:N2 tzc are cross-linked by 4,4′-bpy. Magnetic investigations on 1-3 revealed intramolecular ferromagnetic coupling through the double N-N bridges with intermolecular ferromagnetic or antiferromagnetic interactions. The interaction through the mixed N-N and μ2-Ocarboxylate bridges in 4 is antiferromagnetic.  相似文献   

6.
Three new coordination compounds with 4-sulfophthalic acid (H3SPA) ligand, namely {[Pb3(4-SPA)2(H2O)](H2O)}n (1), [Mn(4,4′-bpy)2(H2O)4][Mn2(4-SPA)2-(4,4′-bpy)4(H2O)4]·7.5(H2O) (2) and Cu2(4-HSPA)2(2,2′-bpy)2(H2O)2 (3) (4,4′-bpy = 4,4′-bipyridine and 2,2′-bpy = 2,2′-bipyridine), have been synthesized. The structures exhibit different dimensionality depending on the nature of the metal ions and/or the ancillary ligands. Compound 1 has a 2D layered architecture constructed from one-dimensional inorganic lead(II) oxygen chains containing tetranuclear [Pb42-O)4] cluster. Compound 2 has a dinuclear manganese [Mn2(4-SPA)2(4,4′-bpy)4(H2O)4] motif charged with mononuclear [Mn(4,4′-bpy)2(H2O)4]2+ cation. Compound 3 is a discrete dinuclear copper(II) structure that linked by extensive hydrogen bonds to form a three-dimensional supramolecular structure. In the solid state, compound 1 exhibits blue photoluminescence with the maximum at 432 nm upon excitation at 350 nm. The temperature-dependent magnetic susceptibility data of 2 have been investigated. The Curie constant C and Weiss constant θ are 3.14 emu K mol−1 and −2.09 K, respectively, revealing antiferromagnetically magnetic interactions between the Mn2+ ions. In addition, these compounds are characterized by powder X-ray diffraction, IR, elemental analysis, and thermogravimetric analysis.  相似文献   

7.
2,6-Dimethyl-4-phenylpyridine-3,5-dicarboxylic acid (H2mppdc, H2L) is firstly employed in coordination chemistry. Two metal-organic coordination polymers with a general formula of M2L2(4,4′-bpy)x(H2O)4−2x (M = Zn or Co, x = 1 or 2) are assembled from H2L, 4,4′-bipyridine, zinc and cobalt salt under hydrothermal conditions, and characterized by single-crystal X-ray diffraction analyses. Of the crystal structures of title compounds, L ligands, limited in the environment from 4,4′-bipyridine, array in head-to-head and head-to-tail modes which are corresponding to the 1D (1) and 3D (2) polymeric structures, respectively. Interesting disorders occur in the crystal lattice of compound 1. And compound 2 has a 3D 42 · 610 · 83 topology. Solid-state H2L and 1 have expected photoluminescence at room temperature.  相似文献   

8.
Three new Cu(II) complexes of formula [Cu(L1)(pyz)(CH3OH)]ClO4 (1), [Cu(L1)(4,4′-bpy)(ClO4)]·0.5H2O (2) and [{Cu(L2)(ClO4)}2(μ-4,4′-bpy)] (3) have been synthesised by using pyrazine (pyz) and 4,4′-bipyridine (4,4′-bpy) and tridentate O,N,O-donor hydrazone ligands, L1H and L2H, obtained by the condensation of 1,1,1-trifluoro-2,4-pentanedione with salicyloylhydrazide and benzhydrazide, respectively. The ligands and their complexes have been characterized by elemental analyses, FT-IR, and UV-Vis spectroscopies. Single crystal X-ray structure analysis evidences the metal ion in a slightly deformed square pyramidal geometry in all the complexes. However complexes 1 and 2 are mononuclear with pyz and 4,4′-bpy, respectively, showing an unusual monodentate behavior, while complex 3 is dinuclear with 4,4′-bpy adopting the typical bridging coordination mode. Self assembly of the complex units by hydrogen bonding interactions produces one-dimensional arrangement in each crystal packing. The magnetic characterization of complex 3 indicates a weak antiferromagnetic exchange interaction between the Cu(II) ions (J = −0.96 cm−1) mediated through the long 4,4′-bpy bridge. Electrochemical behavior of the complexes is also discussed.  相似文献   

9.
Four new fluconazole-bridged zinc(II) and cadmium(II) complexes with dicarboxylate co-ligands, namely [Zn(HFlu)(TPA)]n (1), {[Cd(HFlu)2(TPA)]·2CH3OH}n (2), [Zn(HFlu)2(Suc)(H2O)2]·H2O (3), and [Cd(HFlu)2(Suc)(H2O)2]·H2O (4), have been synthesized and characterized by elemental analysis, IR, TG, and single-crystal X-ray diffraction (HFlu = 2-(2,4-difluorophenyl)-1,3-bis(1,2,4-triazol-1-yl)-propan-2-ol, H2TPA = terephthalic acid, and H2Suc = succinic acid). Complex 1 displays a 2-D corrugated network with common (4,4) topology, in which two types of grids constructed by two bridging TPA dianions and two HFlu ligands are found. Complex 2 shows an unusual (3,6) coordination layer consisting of alternative PMPM Cd-HFlu helical chains in which the Cd(II) nodes are also fixed by terephthalate dianions in a cis fashion. The isostructural complexes 3 and 4 have 20-membered dimeric macrocyclic motifs with the Zn···Zn and Cd···Cd distances of 11.258(2) and 11.528(2) Å, respectively. The fluorescence and thermal stability of complexes 1-4 have also been investigated.  相似文献   

10.
Two new Mn(II) coordination polymers with bis(5-tetrazolyl)methane (H2btm), [Mn(btm)(phen)(H2O)] · H2O (1) and [Mn(btm)(2,2′-bpy)] · 1.5H2O (2), have been synthesized and their structures determined by X-ray diffraction. In complex 1, the btm ligands assume the μ2-1,1′:4 coordination mode and interlink Mn(II) ions into infinite one-dimensional chains. The chains are assembled into a three-dimensional architecture via hydrogen bonds and π-π interactions. For 2, Mn(II) ions are connected by btm ligands in the μ3-1,1′:2:3′ mode to produce two-dimensional (6,3) coordination network. Magnetic investigations revealed that interactions through the btm bridges in both 1 and 2 are antiferromagnetic.  相似文献   

11.
The hydrothermal reactions of CuSO4 · 5H2O, a phosphonate ligand and an appropriate aromatic nitrogen heterocycle yield a series of materials of the Cu(II)/phosphonate/nitrogen ligand donor family. Two of the materials [Cu(2,2′-bpy)(HO3PCH2CH2CH2PO3H)] (1) and [Cu(4,4′-bpy)(H2O)2(HO3PCH2CH2CH2CH2PO3H)] (2) are two-dimensional, while [{Cu(2,2′-bpy)}2(O3PC6H4PO3)] · 8H2O (3 · 8H2O) is three-dimensional. When 1,3,5-benzenetricarboxylic acid is introduced as a reactant, the one-dimensional material [Cu(2,2′-bpy){OC6H2(CO2H)3}(HOPC6H5)] (4) is isolated. This is an example of an in situ hydrothermal ligand transformation in which the 1,3,5-benzene tricarboxylic acid is hydroxylated to give 1,3,5-benzene tricarboxylic acid-2-hydroxide. Compound 5 [Cu(terpy)(HO3PC6H4PO3H] is molecular.  相似文献   

12.
A Co-monosubstituted Keggin polyoxometalate with an antenna ligand linked to the Co(II) center with a Co(II)-containing cation has been prepared. The title compound, formulated as {Co(H2O)4(4,4′-bpy)}2(4,4′-Hbpy)2[SiW11Co(4,4′-bpy)O39] · 5H2O (1) (4,4′-bpy = 4,4′-bipyridine), was synthesized and characterized by elemental analysis, IR spectra, TG analysis, X-ray single crystal structure analysis and magnetic measurements. As far as we know, the title compound represents the first Co(II) substituted Keggin polyoxometalate with an antenna ligand structurally and magnetically characterized.  相似文献   

13.
A series of coordination polymers have been prepared by the combination of flexible ligand 1,1′-biphenyl-2,2′-dicarboxylic acid (H2dpa) and different types of nitrogen-containing ligands, with various metal ions such as Co(II), Zn(II) and Cd(II). The single-crystal structure analyses reveal that the above complexes possess different structure features with the introduction of different nitrogen-containing ligands. When auxiliary linear ligand 4,4′-bipyridine (4,4′-bpy) is introduced, two-dimensional layered complex, [Co2(dpa)2(4,4′-bpy)2(H2O)]n (1) is formed. Whereas if chelating ligand, 1,10-phenanthroline (1,10′-phen) and 2,2′-bipyridine (2,2′-bpy) are introduced, one-dimensional complex [Zn(dpa)(1,10′-phen)]n (2) and discrete complexes [Co2(dpa)2(2,2′-bpy)2(H2O)2] (3), [Co3(dpa)3(1,10′-phen)6(H2O)2] (4), [Cd(dpa)(1,10′-phen)2][(H2dpa)2(H2O)2] (5) are synthesized. To our interest, 1 and 2 crystallize in homochiral spacegroup. Furthermore, the magnetic property of complex 1 and the fluorescent properties of complexes 2 and 5 are studied.  相似文献   

14.
Hydrothermal synthesis has afforded cobalt 5-substituted isophthalate complexes with 4,4′-dipyridylamine (dpa) ligands, showing different dimensionalities depending on the steric bulk and hydrogen-bonding facility of the substituent. [Co(tBuip)(dpa)(H2O)]n (1, tBuip = 5-tert-butylisophthalate) is a (4,4) grid two-dimensional coordination polymer featuring 2-fold parallel interpenetration. [Co(MeOip)2(Hdpa)2] (2, MeOip = 5-methoxyisophthalate) is organized into 3-fold parallel interpenetrated (4,4) grids through strong N-H+?O hydrogen bonding. {([Co(OHip)(dpa)(H2O)3])3·2H2O}n (3, OHip = 5-hydroxyisophthalate) possesses 1-D chain motifs. The 5-methyl derivative {[Co(mip)(dpa)]·3H2O}n (4, mip = 5-methylisophthalate) has a 3-D 658 cds topology. {[Co(H2O)4(Hdpa)2](nip)2·2H2O} (5, nip = 5-nitroisophthalate) and {[Co(sip)(Hdpa)(H2O)4]·2H2O} (6, sip = 5-sulfoisophthalate) are coordination complexes. Antiferromagnetic superexchange is observed in 1 and 4, with concomitant zero-field splitting. Thermal decomposition behavior of the higher dimensionality complexes is also discussed.  相似文献   

15.
Three water-soluble zinc complexes, [Zn(Cbp)2Br2] (1) (Cbp = N-(4-carboxybenzyl)pyridinium), {[Zn(BCbpy)2(H2O)4]3Br6·2(BCbpy)·2(4,4′-bipy)} (2) (BCbpy = 1-(4-carboxybenzyl)-4,4′-bipyridinium) and {[Zn4(Bpybc)6(H2O)12](OH)8·9H2O}2n (3) (Bpybc = 1,1′-bis(4-carboxybenzyl)-4,4′-bipyridinium), were synthesized and characterized by IR, elemental analysis and single-crystal X-ray crystallography. In complex 1, the central Zn atom adopts a distorted tetrahedral coordination geometry that is formed from two unidentate Cbp ligands and two Br atoms. For complex 2, the Zn atom in [Zn(BCbpy)2(H2O)4]2+ is strongly coordinated by four water molecules and two N atoms from two BCbpy ligands, hence forming an octahedral geometry. In complex 3, each Bpybc ligand bridges two [Zn(H2O)3]2+ units through two terminal carboxylate groups in a monodentate coordination mode, thus forming a flowerlike two-dimensional network. Agarose gel electrophoresis (GE) and ethidium bromide (EB) displacement experiments indicated that complex 3 was capable of converting pBR322 DNA into open circular (OC) and linear forms, and exhibited high binding affinity toward calf-thymus DNA. MTT assay showed that complex 3 displayed inhibitory activities toward the proliferation of lung adenocarcinoma A549 and mouse sarcoma S-180 cells, with the IC50 values being 27.3 and 48.8 μM, respectively.  相似文献   

16.
Four novel metal coordination polymers, [Cd(dpa)(H2O)]n (1), [Cd(dpa)(2,2′-bipy)]n (2), {[Cd2(dpa)2(4,4′-bipy)3](4,4′-bipy)(H2O)2}n (3) and [Cd(dpa)(bim)2(H2O)]}n (4) (H2dpa = 2,4′-biphenyl-dicarboxylic acid, 2,2′-bipy = 2,2′-bipyridine, 4,4′-bipy = 4,4′-bipyridine, bim = benzimidazole), have been synthesized and structurally characterized by elemental analysis, IR and X-ray diffraction. Single-crystal X-ray analyses reveal that the 2,4′-diphenic acids acts as bridging ligands, exhibiting rich coordination modes to link metal ions: bis-monodentate, bidentate chelating, chelating/bridging, monoatomic bridging and monodentate modes. In addition, the luminescent properties for compound 1-4 are also investigated in this work.  相似文献   

17.
Hua Jin 《Inorganica chimica acta》2007,360(10):3347-3353
Three new organic-inorganic hybrid compounds [CuI(2,2′-bipy)(4,4′-bipy)0.5]2[CuI(2,2′-bipy)(4,4′-Hbipy)][CuI(4,4′-bipy)]2[P2W18O62] · 3H2O (1), [CuI(2,2′-bipy)(4,4′-bipy)0.5]2[CuI(4,4′-bipy)]2[PW12O40] · 0.25H2O (2), and[CuI(4,4′-bipy)]3[PMo12O40] · en · 3H2O (3) (2,2′- bipy = 2,2′-bipyridine, 4,4′-bipy = 4,4′-bipyridine), have been hydrothermally synthesized. Compound 1 represents the first 1D ladderlike structure formed by Dawson-type polyoxoanion [P2W18O62]6− and coordination polymer with mixed 4,4′-bipy and 2,2′-bipy ligands. The novel structure of 2 is composed of 1D hybrid zigzag chains linked by chains into a 3D framework. In compound 3, the [PMo12O40]3− clusters are hung on chains to form a new 1D chain.  相似文献   

18.
One-dimensional {[Cu2(dppa)2(4,4′-bipy)(CH3CN)2](BF4)2 · 2CH3CN}n (1), two-dimensional {[Cu2(dppa)(4,4′-bipy)2(CH3CN)2](BF4)2 · 4CH2Cl2 · 4H2O}n (2) and three-dimensional {[Cu2(dppa)(4,4′-bipy)3](BF4)2 · 2CH2Cl2 · 3CH3CN · 3H2O}n (3) polymeric complexes have been prepared by self-assembly of [Cu(MeCN)4]BF4, Ph2PCCPPh2 (dppa) and 4,4′-bipyridine (4,4′-bipy) in a 2:2:1, 1:1:1 and 2:2:3 molar ratio, respectively. The structures of 1-3, determined by an X-ray diffraction study, reveal a linear spring-like architecture for 1, a planar honeycomb grid for 2 and an interlocked adamantoid network for 3.  相似文献   

19.
Reactions of AgClO4, Zn(CH3COO)2 · H2O and CuI with the ligand 4,4′-dipyridylsulfide (dps) in 1:1 ratio give rise to coordination polymers 1-3 and 5, the structures of which were characterized by X-ray crystallography. Polymers [Ag2(dps)2](ClO4)2 · MeCN (1) and [Ag2(dps)22-MeCN)(MeCN)](ClO4)2 · MeCN · H2O (2) are pseudo-supramolecular isomers, differing from each other in the coordination geometry of silver atom and the packing pattern. Both 1 and 2 are zigzag coordination polymers bridged by weak Ag?Ag, Ag?S or Ag?NC-CH3 interactions to form double stranded coordination polymers. While [Zn(dps)(CH3COO)2] (3) is a zigzag single stranded coordination polymer, [Zn(dps)2(H2O)2](ClO4)2 · H2O (4) is an unusual mononuclear complex with a box-like structure. Interesting intermolecular hydrogen bonding present in the compounds 3 and 4 leads to 3D hydrogen-bonded network structure.Coordination polymer [Cu2I2(dps)2] (5) is a non-interpenetrating (4,4) net. Photoluminescence properties of the compounds 1-5 have been examined in solid states at room temperature. These compounds have been found to exhibit yellow and blue photoluminescence.  相似文献   

20.
Reaction of ferrocenyl carboxylate H2bfcs with Cd(Ac)2 · 2H2O (H2bfcs = 1,1′-bis(3-carboxy-1-oxopropyl)ferrocene) gives the mononuclear tetrahydrate precursor Cd(Hbfcs)2(H2O)4 (1). Investigation on the substitution reactions of 1 with imidazole or 2,2′-bpy afforded two one-dimensional (1D) complexes {[Cd2(bfcs)2(C3H4N2)6] · 4H2O}n (2) and {[Cd(bfcs)(2,2′-bpy)(H2O)] · 2H2O}n (4) (2,2′-bpy = 2,2′-bipyridine), respectively. However, the one-step reactions of H2bfcs, Cd(Ac)2 · 2H2O with imidazole or 2,2′-bpy result in the formation of two different 1D complexes {[Cd(bfcs)(C3H4N2)2] · CH3OH · 2H2O}n (3) and [Cd(bfcs)(CH3OH)]n (5). It can be seen from the results that applying different synthetic routes produce dissimilar complexes from however the same materials and under the same reaction conditions. In addition, investigations of differential pulse voltammetry of these four 1D complexes indicate that their half-wave potentials are slightly higher than that of H2bfcs.  相似文献   

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