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1.
Two coordination polymers, {[Zn(dpb)(3-bpmp)0.5]·1.5(DMF)}n (1) and [Zn(dpb)(4-bpmp)]n (2) (H2dpb = 1,3-di(4′-carboxyl-phenyl)benzene, 3-bpmp = 1,4-bis(3-pyridylmethy)piperazine, 4-bpmp = 1,4-bis(4-pyridylmethy)piperazine and DMF = N,N-dimethylformamide), were solvothermally synthesized and characterized. Tuning the difference of N-donor ligands, we obtained 1 and 2 which display different topological nets. Complex 1 features a 6-connected topological net and 2 shows a 4-connected three-fold interpenetrated framework. Luminescent properties of 1 and 2 are investigated at room temperature.  相似文献   

2.
Two 3-D MOFs, {[Co2(oba)2(bmip)]·DMA}n (1) and [Cd(1,3-bdc)(bmip)]n (2), where H2oba = 4,4′-oxybis(benzoic acid), 1,3-bdc = isophthalic acid and bmip = 1,3-bis(2-methylimidazolyl)propane, were synthesized under solvothermal conditions and characterized by single-crystal X-ray diffraction, powder XRD, FT-IR, TGA, and elemental analysis. Complex 1 features a 3-D→3-D twofold interpenetrating framework, and topological analysis shows the framework can be described as a 6-connected uninodal pcu net having the point symbol (412.63). Complex 2 shows a 3-D→3-D threefold interpenetrating network that can be described as a 4-connected uninodal cds net with (65.8) topology. Gas adsorptions of 1 were carried out, and photoluminescent properties of 1 and 2 were also investigated at room temperature.  相似文献   

3.
Herein we report the synthesis and characterization of trans-[RuIICl2(PPh3)3] with potentially tridentate Schiff bases derived from 5,6-diamino-1,3-dimethyl uracil (H2ddd) and two 2-substituted aromatic aldehydes. In the diamagnetic ruthenium(II) complexes, trans-[RuCl(PPh3)2(Htdp)] (1) {H2tdp = 5-((thiophen-3-yl)methyleneamino)-6-amino-1,3-dimethyluracil} and trans-[RuCl(PPh3)2(Hsdp)] (2) {H2sdp = 5-(2-(methylthio)benzylideneamino)-6-amino-1,3-dimethyluracil}, the Schiff base ligands (i.e. Htdp and Hsdp) act as mono-anionic tridentate chelators. Upon reacting 5-(2-hydroxybenzylideneamino)-6-amino-1,3-dimethyluracil (H3hdp) with the metal precursor, the paramagnetic complex, trans-[RuIVCl2(ddd)(PPh3)2] (3), was isolated, in which the bidentate dianionic ddd co-ligand was formed by hydrolysis. The metal complexes were fully characterized via multinuclear NMR-, IR-, and UV–Vis spectroscopy, single crystal XRD analysis and conductivity measurements. The redox properties were probed via cyclic voltammetry with all complexes exhibiting comparable electrochemical behavior with half-wave potentials (E½) at 0.70 V (for 1), 0.725 V (for 2), and 0.68 V (for 3) versus Ag|AgCl, respectively. The presence of the paramagnetic metal center for 3 was confirmed by ESR spectroscopy.  相似文献   

4.
A preliminary study on Echinops giganteus (Asteraceae) showed that the methanolic extract has interesting cytotoxicities against a panel of cancer cell lines. From this extract, a lignan, a flavonoid and a polyacetylenic thiophene identified were three times less cytotoxic than the extract. In the search of the metabolites responsible for the bioactivity, a new harvested E. giganteus was subjected to a phytochemical study using chromatographic methods. In the course of the work, two new compounds: a brominated oleanolide (1) and a tetrahydrofurano-ceramide (2) were obtained along with β-amyrin acetate (3), 2-(penta-1,3-diynyl)-5-(4-hydroxybut-1-ynyl)-thiophene (4), 2-(penta-1,3-diynyl)-5-(3,4-dihydroxybut-1-ynyl)-thiophene (5) and 4-hydroxy-2,6-di-(3′,4′-dimethoxyphenyl)-3,7-dioxabicyclo-(3.3.0)octane (6). Their structures were determined on the basis of NMR spectroscopy and mass spectrometry data in conjunction with those reported in the literature. The cytotoxicity of 1, 2 and 5 was evaluated by employing resazurin assay against a panel of cancer cell lines with IC50 values in range 6.12 ± 0.46–46.96 ± 3.61 μM.  相似文献   

5.
Four Cd(II)- and Cu(II)-containing coordination polymers (CPs) based on a multidentate N-donor ligand and varied dicarboxylate anions, [Cd(3,3′-tmbpt)(p-bdc)]·2.5H2O (1), [Cd(3,3′-tmbpt)(m-bdc)]·2H2O (2), [Cu(3,3′-tmbpt)(m-bdc)]·H2O (3), and [Cu(3,3′-tmbpt)(p-bdc)]·2H2O (4), where 3,3′-tmbpt = 1 ? ((1H-1,2,4-triazol-1-yl)methyl)-3,5-bis(3-pyridyl)-1,2,4-triazole, p-H2bdc = 1,4-benzenedicarboxylic acid, and m-H2bdc = 1,3-benzenedicarboxylic acid, have been prepared hydrothermally. The structures of the compounds were determined by single-crystal X-ray diffraction analyses and further characterized by infrared spectra and elemental analyses. Compound 1 exhibits a 3-D twofold interpenetrating framework with a 65·8 CdSO4 topology. Compound 2 is a 2-D layer containing meso-helical chains with a 44·62 sql topology. Compound 3 shows a 1-D → 3-D interdigitated architecture while 4 displays a 2-D → 3-D interdigitated architecture. The structural differences of the compounds indicate that the dicarboxylate anions and the central metal ions play important roles in the resulting structures of CPs. Optical band gaps and solid-state photoluminescent properties have also been studied.  相似文献   

6.
Three novel coordination polymers, [Co(NH2-Aip)(H2Bibim)] n (1), [Co(NH2-Aip)(HBibimop)] n  √ nH2O (2) and [Mn(NH2-Aip) √ H2O] n  √ 2nH2O (3) with NH2-Aip and similar benzimidazole derivative ligands (NH2-Aip = 5-aminoisophthalic acid, H2Bibim = 2,2′-bibenzimidazole and HBibimop = 1,3-bis(benzimidazol-2-yl)-2-oxapropane), have been synthesised under hydrothermal conditions and structurally characterised by single-crystal X-ray diffraction analysis, elemental analysis and IR spectroscopy. 5-Aminoisophthalic acid ligand adopts μ2-, μ3- and μ4-bridge coordination fashion and benzimidazole derivatives exist as terminal- and bridge-mode in complexes 13. The intricate hydrogen bonds and π–π stacking interactions in supramolecular framework are discussed. Using the combination of ultraviolet–visible absorption titration and fluorescence spectra, the experimental results show that complexes 1 and 2 bind to DNA in an intercalative mode and their DNA-binding constants (K b ) are also found.  相似文献   

7.
The structural characterization of tetranuclear cage-type cadmium(II) carboxylate [Cd4(2-cpida)2(2,2′-bpy)6]·(2,2-bpy)·(ClO4)·3H2O (1) (2-H3cpida = N-(2-carboxyphenyl)iminodiacetic acid, 2,2′-bpy = 2,2′-bipyridine) is described. H-bonding interactions between three lattice water molecules form a V-shaped trimer (H2O)3, which is stabilized by 1. In addition, luminescence investigations revealed that 1 shows enhanced emissions as compared with free 2-H3cpida in the liquid state.  相似文献   

8.
Three mono-, bi- and tetranuclear copper(I) complexes, [Cu(phen)(triphos-O)]BF4 (1) (phen = 1,10-phenanthroline, triphos = 1,1,1-tris(diphenylphosphinomethyl)ethane), [Cu2(bipy)(triphos)2](BF4)2 (2) (bipy = 4,4′-bipyridine), and [Cu4(MeOC^N^N)4(triphos)2(bipy)](BF4)4 (3) (MeOC^N^N = 6-(4-methoxyphenyl)-2,2′-bipyridine), have been synthesized and characterized by NMR spectroscopy, electrospray ionization, and matrix-assisted laser desorption ionization time-of-flight mass spectrometries, elemental analysis, and X-ray crystal analysis. The crystal structure investigation revealed the copper ions of the complexes have pseudo-tetrahedral coordination geometry. The electronic absorption spectra of 1, 2, and 3 contain low-energy bands at 350–500 and 400–650 nm, which are assigned to d(Cu) → π*(phen or bipy) and a mixture of d(Cu) → π*(MeOC^N^N) and d(Cu) → π*(bipy) transitions, respectively. Complex 2 displays a strong, long-lived solid-state emission with a maximum at 555 nm and lifetime of 13.6 μs at room temperature. Photoinduced electron-transfer properties of 2 and 3 involving nanosecond time-resolved absorption spectroscopy and electron spin resonance techniques were studied.  相似文献   

9.
Abstract

A β-diketonate mononuclear dysprosium compound, [Dy(TFNB)3(bpy)] (1) (TFNB = 4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedione, bpy = 2,2′-bipyridine), has been prepared and structurally and magnetically characterized. X-ray crystallographic analysis reveals that 1 contains two crystallographically equivalent Dy(III) ions of which the eight-coordinate geometries uniformly behave as distorted square antiprismatic configurations (D4d). Magnetic investigations demonstrate that 1 displays dual relaxation processes of SMMs behavior with the effective barrier (ΔE/kB) of 23.44 K under 1200 Oe DC field, corresponding to the coexistence of two metal centers in the structure of the compound. The comparative studies of some Dy(III)-based SIMs with TFNB ligand have been conducted as well. Ab initio studies demonstrate that the Kramers doublet ground state is predominantly axial with the gz tensors of two Dy(III) fragments matching the Ising-limit factor (20) anticipated for the pure MJ = ±15/2 state.  相似文献   

10.
Thiopurines bis(S-8-thiotheophylline)methane (MBTTH2), 1,2-bis(S-8-thiotheophylline)ethane (EBTTH2), and 1,3-bis(S-8-thiotheophylline)propane (PBTTH2) were reacted with [RuClCp(mPTA)2](CF3SO3)2 in water to afford the bis-ruthenium complexes [{RuCp(mPTA)2}2-μ-(L-κN7,N′7)](CF3SO3)4 (1: L = MBTT; 2: L = EBTT; 3: L = PBTT), which have been characterized by elemental analysis, IR, and multinuclear NMR (1H, 13C{1H}, 31P{1H} and 19F{1H}) spectroscopy). Diffusion experiments for 1 were carried out. Proposed structures for the three complexes were also supported by theoretical calculations. Cyclic voltammetry showed that these complexes are characterized by two one-electron irreversible oxidative response (RuII – RuII/RuIII – RuII; RuIII – RuII/RuIII – RuIII). Complexes showed poor antiproliferative activity against cisplatin-sensitive T2 human cell line and the cisplatin-resistant SKOV3 cell line.  相似文献   

11.
Three coordination polymers [Zn(μ3-HNIDC)(CH3OH)]n (H3NIDC = 2-(2-naphthyl)-1H-imidazole-4,5-dicarboxylic acid) (1), [Mn(μ2-HNIDC)(4,4′-bipy)]n (4,4′-bipy = 4,4′-bipyridine) (2) and [Mn22-HNIDC)2(phen)2]n (phen = 1,10-phenanthroline) (3) have been solvothermally synthesised and structurally characterised by single-crystal X-ray diffraction, elemental analyses, thermal analyses and IR spectra. Polymer 1 displays a three-dimensional open architecture with one-dimensional (1D) channels. Polymer 2 exhibits a sheet structure containing infinite rectangles. Polymer 3 presents a 1D wave chain structure. The solid-state photoluminescence of 1 has been investigated as well.  相似文献   

12.
Complexes of [Zn(ibup)2(4,4′-bipy)]n 1, [Zn(ibup)2(phen)] 2, [Zn(ibup)2(2,9-dmphen)] 3, [Zn(ibup)2(1,2-dmimidazole)2] 4, and [Zn(ibup)2(2-am-6-picoline)2] 5 (ibu = ibuprofen, 4,4′-bipy = 4,4′-bipypyridine, phen = 1,10-phenanthroline, 2,9-dmephen = 2,9-dimethyl-1,10-phenanthroline, 1,2-dmimidazole = 1,2-dimethylimidazole, and 2-am-6-picoline = 2-amino-6-picoline) were prepared and characterized. The crystal structure of 1 was determined by single-crystal X-ray diffraction. The in vitro anti-bacterial activities for the complexes against Gram-positive (Micrococcus luteus, Staphylococcus aureus and Bacillus subtilis) and Gram-negative (Escherichia coli, Klebsiella pneumonia and Proteus mirabilis) bacteria were done using the agar well-diffusion method. Complexes 13 showed anti-bacterial activity against Gram-positive bacteria, while 4 and 5 did not exhibit anti-bacterial activity. Complexes 2 and 3 were selected for further studies. Complexation of zinc-ibuprofen with phen as in 2 decreased the anti-bacterial activity against most of the bacteria used. The complexation in 3 decreased the anti-bacterial activity in Gram-positive bacteria but for Gram-negative bacteria, the overall anti-bacterial activity of uncoordinated 2,9-dmphen was enhanced upon coordination with zinc ibuprofen.  相似文献   

13.
Two new metal–organic compounds, [Ag2(HADC)2(bimh)] (1) and [Cd(ADC)(bpp)]n (2) [H2ADC = 1,3-adamantanedicarboxylic acid, bimh = 1,6-bis(2-methyl-imidazole-1-yl)hexane, bpp = 1,3-bis(4-pyridyl)propane], have been synthesized and characterized. Compound 1 exhibits a discrete symmetric unit with 0D→2D interpenetrating structure. Compound 2 crystallizes in a chiral space group P212121 and presents a threefold interpenetrated 3D diamondoid network containing three helical chains. Thermal stability, X-ray powder diffraction, and luminescence for 1 and 2 are also measured and discussed.  相似文献   

14.
Abstract

A novel manganese compound, [Mn2(μ1,3-6-CH3-2-NH2C6H4COO)2(bipy)4](ClO4)2 (bipy = 2,2′-bipyridine), was synthesized and used as a catalyst precursor in the oxidation of alkenes and primary alcohols to corresponding aldehydes, ketones, and acids. The six-coordinate compound has a binuclear structure in which two Mn(II) ions adopt a syn-anti μ1,3-bridging mode with two carboxylate groups and two chelated bipy ligands. The compound exhibits good activity in the oxidation of cyclohexene to 2-cyclohexene-1-one as the major product (93% conv. in 3 h, 79.3% selectivity) and of cinnamyl alcohol to cinnamaldehyde as the major product with 46% selectivity (100% conv. in 1.5 h) with tert-butyl hydroperoxide (TBHP) in acetonitrile at 70 °C. Furthermore, the catalase-like activity of the compound was studied in different solvents (acetonitrile, methanol, Tris-HCl buffer; TOF = 29,910 h?1 in Tris-HCl buffer).  相似文献   

15.
Two coordination polymers with 5-aminoisophthalic acid (H2aip), [Ni(μ-aip)(H2O)2(tmeda)]n (1) and {H2dap[Zn2(μ-aip)(μ3-aip)2]?9H2O}n (2) (H2aip = 5-aminoisophthalic acid, tmeda = N,N,N′-N′-tetramethylethylenediamine, dap = 1,3-diaminopropane) have been synthesized. Elemental and thermal analyses, magnetic susceptibilities, IR, AAS, mass and UV–vis spectroscopic studies have been performed to characterize the compounds. Nickel(II) has octahedral geometry by two oxygens of different carboxylates, bidentate, tmeda as bidentate chelating and two water ligands. Zn(II) has tetrahedral geometry by three oxygens of different carboxylate groups and one nitrogen by amine of aip. 1 crystallizes in the orthorhombic crystal system with space group Pccn and 2 in monoclinic crystal system with space group P21/c. Complex 2 exhibits photoluminescence properties in the solid state at room temperature. This study determined the susceptibility patterns of 1 and 2 against bacterial, yeast and mold micro-organisms. Antimicrobial activities were done on 12 different micro-organisms using the micro-dilution method. Tested microbial species were inhibited by 1 with a Minimum inhibitory concentrations (MIC) of 375–3000 μg mL?1. Compound 2 showed antimicrobial activities against tested micro-organisms with a MIC of 188–1500 μg mL?1. Compound 2 showed antibacterial activity against Legionella pneumophila sg1 375 μg mL?1 (MIC value).  相似文献   

16.
Metal carboxylate complexes possess different carboxylate coordination modes, e.g. monodentate, bidentate, and bridging bidentate. Five Zn(II) complexes were prepared and characterized in order to examine their coordination modes in addition to their biological activity. The syntheses were started by preparation of [Zn(ibup)2(H2O)2] (1). Then, different nitrogen-donor ligands reacted with 1 to produce [Zn(ibup)2(2-ampy)2] (2), [Zn(ibup)(2-ammethylpy)] (3), [Zn(ibup)(2,2′-bipy)] (4), and [Zn2(ibup)4(2-methylampy)2] (5) (ibup = ibuprofen, 2-ampy = 2-aminopyridine, 2-ammethylpy = 2-aminomethylpyridine, 2,2′-bipy = 2,2′-bipyridine, 2-methylampy = 2-(methylamino)pyridine). IR, 1H NMR, 13C{1H}-NMR and UV–vis spectroscopies were used for characterization. The crystal structures of 2 and 5 were determined by single-crystal X-ray diffraction. Investigation of in vitro antibacterial activities for the complexes against Gram-positive (Micrococcus luteus, Staphylococcus aureus and Bacillus subtilis) and Gram-negative (Escherichia coli, Klebsiella pneumoniae and Proteus mirabilis) bacteria were done using agar well-diffusion method. Complex 1 showed antibacterial activity against Gram-positive bacteria. Complexes 2 and 3 did not exhibit antibacterial activity. Complex 4 showed antibacterial activity and was chosen for further studies to determine the inhibition zone diameter for different concentrations and to set the minimum inhibitory concentration. The antibacterial activity against most of the bacteria was minimized as a result of the complexation of zinc ibuprofen with 2,2′-bipy in 4.  相似文献   

17.
Complexes based on different halogen-substituted nitronyl nitroxide radicals and Cu(II), Cu3(hfac)6(NIT-Ph-F)2 (1) and Cu3(hfac)6(NIT-Ph-Cl)2 (2) (hfac = hexafluoroacetylacetonate; NIT-Ph-F = 2-(4′-fluorophenyl)-4,4,5,5-tetramethyl-imidazoline-1-oxyl-3-oxide; NIT-Ph-Cl = 2-(4′-chlorphenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide), were synthesized and characterized structurally and magnetically. X-ray crystal structure analyses show that 1 and 2 have similar centrosymmetric five-spin structures consisting of three Cu(II) ions bridged by two nitroxide ligands. The Cu(II) is coordinated by six oxygens to form an octahedron, while the five coordination of the terminal Cu(II) ion is square pyramidal. Magnetic measurements reveal strong antiferromagnetic interactions between Cu(II) ions and radicals in 1 (J = ?38.9 cm?1) and weak antiferromagnetic interactions between Cu(II) ions and radicals in 2 (J = ?1.23 cm?1), which may be explained by the bond length of the Cu–Orad (2.468(2) Å) in 1, which is shorter than that (2.514(2) Å) in 2, and the dihedral angle (73.17(1)°) of the plane O7–O8–Cu(2)–O7A–O8A with the moiety O5–N1–C11–N2–O6 in 1 is smaller than (77.82(1)°) in 2.  相似文献   

18.
Four coordination polymers, [CsL1(H2O)2]·H2O (1), [CsL2(H2O)2]·H2O (2), [Rb2(L2)2(H2O)2]·2H2O (3) and [RbL3(H2O)] (4), were synthesized by Cs(I), Rb(I) and 4′-hydroxyisoflavone-3′-sulfonates L1L3 [L1 = 7-methoxy-4′-hydroxyisoflavone-3′-sulfonate, L2 = 7-ethoxy-4′-hydroxyisoflavone-3′-sulfonate, L3 = 7-ethoxy-4′,5-dihydroxyisoflavone-3′-sulfonate]. The crystal structures of 14 were determined by single-crystal X-ray diffraction. The influences of 4′-hydroxyisoflavone-3′-sulfonate ligands and Cs+, Rb+ on their structural features and self-assembly were investigated. The sulfonates of L1L3 not only coordinate with Cs+ or Rb+ directly, but also bridge the organic region and the inorganic region in 14. Non-covalent interactions such as coordination interaction, ππ stacking interaction and hydrogen bonding assembled 14 into 3-D networks together with the electrostatic interactions between Cs+, Rb+ and the sulfonate anions.  相似文献   

19.
Four lanthanide complexes, [La2(2,4-DClBA)6(5,5′-DM-2,2′-bipy)2(H2O)2]·2C2H5OH (1) and [Ln(2,4-DClBA)3(5,5′-DM-2,2′-bipy)(C2H5OH)]2 (Ln = Pr(2), Sm(3), Gd(4); 2,4-DClBA = 2,4-dichlorobenzoate; 5,5′-DM-2,2′-bipy = 5,5′-dimethyl-2,2′-bipyridine), were synthesized and characterized via elemental analysis, infrared spectra and thermogravimetric analysis (TG). The crystal structures of 1 and 2–4 are different; Each La3+ is nine-coordinate adopting a distorted mono-capped square antiprism, while the Ln3+ ions of 2–4 are all eight-coordinate with a distorted square antiprismatic molecular geometry. There are subtle changes in the local coordination geometry of the lanthanide–5,5′-DM-2,2′-bipy complexes. Binuclear 1 complexes are stitched together via two kinds of hydrogen bonding interactions (OH?O and CH?O) to form 1-D chains along the y axis, while the units of 2–4 are stitched together via CH?O to form 1-D chains along the x axis. TG analysis revealed thermal decomposition processes and thermal stabilities of the complexes. The bacteriostatic activities of the complexes were evaluated against Candida albicans, Escherichia coli, and Staphylococcus aureus.  相似文献   

20.
Two pairs of isostructural transition metal coordination polymers, {[Co(L)(H2O)]n} (1) and {[Zn(L)(H2O)]n} (3), {[Co(L)(4,4′-bipy)(H2O)]·H2O}n (2) and {[Zn(L)(4,4′-bipy)(H2O)]·H2O}n (4) (H2L = N-pyrazinesulfonyl-glycine acid and 4,4′-bipy = 4,4′-bipyridine), have been synthesized and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental and thermogravimetric analyses. The structures show that 1 and 3 display 2-D polymeric grid frameworks with a 3-connected (4, 82) topology. 2 and 4 also exhibit a 2-D polymeric grid structure, but are constructed by a 4-connected (4, 4) topology. The adjacent 2-D polymeric grid frameworks for 1–4 are further linked by hydrogen bonding O–H?O interactions to form 3-D supramolecular interweaved orderly networks. The fluorescent properties of 3 and 4 were investigated in the solid state.  相似文献   

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