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1.
DNA targeting macrocyclic dicopper(II) complex, [Cu2L(H2O)2](phen)2(ClO4)2 (L = μ-11,23-dimethyl-3,7,15,19-tetraazatricyclo-[19.3.1.19,13,21] he p t a c o s a-1(24), 2, 7, 9, 11, 13(26), 14, 19, 21(25), 22-decaene-25,26-diol) (2), has been synthesized and characterized. This has been synthesized by reacting a Robson type macrocyclic precursor dicopper(II) complex [Cu2L(H2O)2](ClO4)2 (1) and 1,10-phenanthroline in ethanol. Solution ESR, electronic, and ESI-MS spectral studies suggest that 1,10-phenanthroline replaces coordinated water in 1, giving 2. The influence of the phenanthroline on DNA binding, cleavage, and anticancer properties of 2 have been investigated. Complex 2 displays better DNA binding and cleavage than 1. The dicopper(II) complexes 1 and 2 show cytotoxicity in human cervical HeLa cancer cells, giving IC50 values of 79.41 and 15.82 μM, respectively. Antiproliferative properties of 1 and 2 were confirmed by Trypan Blue exclusive assay and lactate dehydrogenase enzyme level in HeLa cancer cell lysate and content media.  相似文献   

2.
Three multi‐dentate 1, 2,4‐triazole derivative ligands containing different 4‐substituted groups, namely N‐1, 2,4‐triazol‐4‐yl(pyridin‐3‐yl)methylenimine (L1), N‐1, 2,4‐triazol‐ 4‐yl(pyridin‐4‐yl)methylenimine (L2), and 4‐(2‐pyridine)‐1, 2,4‐triazole (L3) were used to isolate five iron(II) and zinc(II) coordination frameworks, [Zn(μ2‐L1)Cl2] ( 1 ), [Zn(μ2‐L2)Br2] ( 2 ), [Fe(L1)2(NCS)2(H2O)2] ( 3 ), [Fe(L3)2(dca)2(H2O)2] ( 4 ), and [Fe(L3)22‐dca)] ( 5 ) (dca = dicyanamide anion). When different zinc(II) salts were used to react with L1 and L2 under solvothermal conditions, two one‐dimensional (1D) zinc(II) coordination frameworks 1 and 2 containing four‐coordinate central zinc(II) atoms were isolated. 1 is a 3D achiral supra‐molecular framework, whereas 2 is a 3D chiral supra‐molecular framework containing helical chains on a 21 axis. 3 is a mono‐nuclear iron(II) coordination framework containing six‐coordinate central FeII atoms. When L3 was employed, mono‐nuclear iron(II) framework 4 and 1D iron(II) chain 5 could be isolated when different amounts of Nadca were introduced into the reaction system. Variable‐temperature magnetic susceptibility data of 3 – 5 were recorded in the 2–300 K temperature range indicating weak anti‐ferromagnetic interactions. The solid‐state luminescent properties of coordination polymers 1 and 2 were also investigated at room temperature.  相似文献   

3.
The enzyme tyrosinase contains a reactive side-on peroxo dicopper(II) center as catalytically active species in C−H oxygenation reactions. The tyrosinase activity of the isomeric bis(μ-oxo) dicopper(III) form has been discussed controversially. The synthesis of bis(μ-oxo) dicopper(III) species [Cu2(μ-O)2( L1 )2](X)2 ([ O1 ](X)2, X=PF6, BF4, OTf, ClO4), stabilized by the new hybrid guanidine ligand 2-{2-((dimethylamino)methyl)phenyl}-1,1,3,3-tetramethylguanidine ( L1 ), and its characterization by UV/Vis, Raman, and XAS spectroscopy, as well as cryo-UHR-ESI mass spectrometry, is described. We highlight selective oxygenation of a plethora of phenolic substrates mediated by [ O1 ](PF6)2, which results in mono- and bicyclic quinones and provides an attractive strategy for designing new phenazines. The selectivity is predicted by using the Fukui function, which is hereby introduced into tyrosinase model chemistry. Our bioinspired catalysis harnesses molecular dioxygen for organic transformations and achieves a substrate diversity reaching far beyond the scope of the enzyme.  相似文献   

4.
On the basis of spectrophotometric studies, it was demonstrated that complexation of hydrobromides of seven alkylated 3,3′-bis(dipyrrolylmethenes) (H2L · 2HBr) with zinc(II) acetate dihydrate in DMF (298.15 K) includes successive steps of formation of binuclear helicates of two types: [Zn2(AcO)2L] (heteroleptic single-helix complex) and [Zn2L2] (homoleptic double-helix complex). An increase in the degree of alkylation of the pyrrole rings of the ligands from 4 to 10 methyl groups induces an increase of overall complexation constants from 7.60 to 13.73. The synthesis of helicates [Zn2L2] was described. The products were studied by elemental analysis and IR, 1H NMR, U/Vis, and fluorescence spectroscopy. The effect of the helicand structure and the solvent nature on the chromophore and fluorescence properties of [Zn2L2] was discussed. The kinetic stability of zinc(II) with decamethyl-substituted 3,3′-bis(dipyrrolylmethene) in HCl-DMF medium was estimated.  相似文献   

5.
A bis(μ-NN′-tetrazolate)-bridged centrosymmetric dinuclear zinc(II) Schiff base complex, [Zn2(L)2(PZTZ)2] (HL is a tridentate Schiff base, 2-(2-(dimethylamino)ethyliminomethyl)-6-ethoxyphenol and HPZTZ is 2-pyrazinyltetrazole), has been synthesized via [3 + 2] cycloaddition of 2-cyanopyrazine and sodium azide in the presence of zinc(II) acetate dihydrate and HL. The structure of the complex is confirmed by single-crystal X-ray diffraction analysis. The complex shows fluorescence.  相似文献   

6.
The reactions of mono-, bis- and tetrapicolyl-p-tert-butylcalix[4]arene derivatives functionalised in the phenolic positions (L 1 L 4 ) with copper(II) acetate resulted in the formation of discrete complexes or extended coordination polymers. The centrosymmetric dimer [Cu2(μ-O2CCH3)4(L 1 )2] 1, obtained with monodentate L 1 , has square pyramidal coordination around the copper centres and a cone conformer of monopicolyl-calix[4]arene acting as an axial ligand, with a molecule of acetonitrile hosted within its cavity. The potentially bidentate L 2 acts as a monodentate ligand, affording the complex [Cu2(μ-O2CCH3)4(L 2 )2] 2, which based on spectroscopic and combustion analysis data has a similar coordination sphere around Cu(II). Compound L 3 bridges two dicopper units in the coordination polymer [Cu2(μ-O2CCH3)4(μ-L 3 )] n 3, with the calixarene hosting a molecule of tetrahydrofuran. Finally, compound L 4 reacts with 4 equivalents of copper(II) acetate, presumably generating a two-dimensional coordination polymer formulated as [{Cu2(μ-O2CCH3)4}2(L 4 )] 4.  相似文献   

7.
The mixed‐ligand metal–organic complex poly[(μ3‐phthalato)[μ2‐3‐(pyridin‐2‐yl)‐1H‐pyrazol‐1‐ido]dicopper(II)], [Cu2(C8H4O4)(C8H6N3)2]n, has been synthesized by the reaction of copper(II) acetate with 2‐(1H‐pyrazol‐3‐yl)pyridine (HL) and phthalic acid. The binuclear chelating–bridging L units are further linked by bridging phthalate ligands into a two‐dimensional network parallel to the (010) plane. The two‐dimensional networks are extended into a three‐dimensional supramolecular architecture viaπ–π stacking interactions.  相似文献   

8.
The oxalato-bridged dicopper(II) complexes [Cu2(μ-ox)(LRR)2(H2O)2(ClO4)2] (1),[Cu2(μ-ox)(LRR)2(CH3COCH3)2(ClO4)2](1a),[Cu2(μ-ox)(LSS)2(H2O)2(ClO4)2] (2) and [Cu2(μ-ox)(LRR)(LSS)2(CH3COCH3)2(ClO4)2] (3) [LRR = (8R,10R)-(-)-[4,5]-pineno2,2′-bipyridine,LSS = (8S,10S)-(+)-[4,5]-pineno-2,2′-bipyridine;ox2= oxalate] were first prepared.A possible mechanism for the formation of the chial dicopper(II) complexes was proposed.Based on elemental analysis,conductance measurement,UV-Vis spectra,CD spectra and X-ray single-crystal diffraction,the oxalato-bridged structures of 1 and 2 were deduced to adopt two Cu(II) ions and the bridged oxalate lying in the nearly same plane.The crystal structures of 1a and 3 reveal that the coordination geometry around each Cu(II) ion is an elongated and distorted octahedron and two axial solvent molecules and two perchlorate ions are anti to each other respectively in both binuclear molecules.The solution CD spectra of 1 and 2 in the visible d-d range show very weak Cotton effects with peaks at 588 and 779 nm,which are approximately of mirror image,suggesting the optical activities may be derived from the vicinal effects of the chiragenic centers at the pinene group of LRR and LSS,respectively.Complex 1 has been characterized by variable-temperature magnetic susceptibility and the data was least-square fitted to the Blenaey-Bowers equation.The exchange integral J was found to be -338.41(4) cm-1,indicating a strong antiferromagnetic interaction between two copper(II) ions.  相似文献   

9.
A novel double helical dicopper(II) complex was synthesized by reaction of a polydentate ligand L = 2,2′‐bipyridyl‐6,6′‐bis(2‐acetylpyrazinohydrazone) with copper(II) perchlorate in CH3CN. The self‐assembling process was studied by UV‐Vis spectrometric titration experiments which revealed the formation of dinuclear complexes [Cu2L2](ClO4)4. The structure of dicopper double‐helicate was confirmed by X‐ray diffractometry. Each copper(II) center occupies a distorted octahedral environment. Variable‐temperature magnetic measurements reveal weak antiferromagnetic interactions between Cu(II) ion centers with J = ?0.63 cm?1.  相似文献   

10.
Mechanistic studies of substrate insertion into dimeric [(NHC)CuH]2 (NHC=N-heterocyclic carbene) complexes with two bridging hydrides have been shown to require dimer dissociation to generate transient, highly reactive (NHC)Cu−H monomers in solution. Using single-crystal to single-crystal (SC-SC) transformations, we discovered a new pathway of stepwise insertion of CO2 into [(NHC)CuH]2 without complete dissociation of the dimer. The first CO2 insertion into dimeric [(IPr*OMe)CuH]2 (IPr*OMe=N,N′-bis(2,6-bis(diphenylmethyl)-4-methoxy-phenyl)imidazole-2-ylidene) produced a dicopper formate hydride [(IPr*OMe)Cu]2(μ-1,3-O2CH)(μ-H). A second CO2 insertion produced a dicopper bis(formate), [(IPr*OMe)Cu]2(μ-1,3-O2CH)(μ-1,1-O2CH), containing two different bonding modes of the bridging formate. These dicopper formate complexes are inaccessible from solution reactions since the dicopper core cleanly ruptures to monomeric complexes when dissolved in a solvent.  相似文献   

11.
One novel triply-bridged dicopper(II) complex formulated as [Cu2(dpa)2(μ-Cl)(μ-OH)(μ-HCOO)]·(ClO4) 1 and two terephthalate anions bridged 2,2′-bipyridine (2,2′-bpy) dicopper(II) complexes with formulae of [Cu2(2,2′-bpy)4(μ-terephthalate)]·(NO3)22 and [Cu2(2,2′-bpy)4(μ-terephthalate)]·(terephthalate) 3, respectively, have been synthesized and characterized by infrared and electrospray mass spectra as well as X-ray single-crystal determination. In addition, thermal properties of all compounds have been studied.  相似文献   

12.
An unexpected polyhydroxyl‐bridged tetranuclear ZnII complex and a benzoquinone compound derived from metal‐ion promoted reactivity of Schiff base ligands were synthesized and characterized. The reaction of zinc(II) acetate dihydrate with oxime‐type Schiff base ligand HL1 [HL1 = 1‐(3‐((3,5‐dibromosalicylaldehyde)amino)phenyl)ethan‐1‐one O‐benzyl oxime] in methanol, acetone, and acetonitrile resulted in the chemoselective cleavage of the C=N bond of the Schiff base HL1, and then the further addition of acetone to two salicylaldehyde molecules derived from cleavage of the C=N bond in situ α,α double aldol reaction promoted by ZnII ions. The newly formed ligands H4L2 coordinate to four ZnII ions forming a defect‐dicubane core structure [ZnII4(H2L2)23‐OCH3)2(μ‐OCH3)2(CH3OH)2] ( 1 ) bridged exclusively by oxygen‐based ligands. The similar ligand HL3 [HL3 = 1‐(3‐((3,5‐dichlorosalicylaldehyde)amino)phenyl)ethan‐1‐one O‐benzyl oxime)] was employed to react with CdII acetate dihydrate under the same reaction conditions. No aldol addition occurred but a unexpected benzoquinone compound 2,5‐bis(((3‐(1‐((benzyloxy)imino)ethyl)phenyl)imino)methyl)‐1,4‐benzoquinone ( 2 ) formed. The results provided interesting insights into one‐pot routes involving in situ reactions act as a strategy for obtaining a variety of polymeric/polynuclear complexes which are inconvenient to obtain from directly presynthesizing the ligands.  相似文献   

13.
A series of dinuclear half-sandwich Ru(II), Os(II) and Ir(III) complexes [Ru2(μ-Ln)(η6-pcym)2Cl2](PF6)2 ( 1 , 4 ), [Os2(μ-Ln)(η6-pcym)2Cl2](PF6)2 ( 2 , 5 ) and [Ir2(μ-Ln)(η5-Cp*)2Cl2](PF6)2 ( 3 , 6 ), based on 4,4′-biphenyl-based bridging Schiff base ligands N,N′-(biphenyl-4,4′-diyldimethylidyne)bis-2-(pyridin-2-yl)methanamine (L1; for 1 – 3 ) and N,N′-(biphenyl-4,4′-diyldimethylidyne)bis-2-(pyridin-2-yl)ethanamine (L2; for 4 – 6 ) is reported; pcym = 1-methyl-4-(propan-2-yl)benzene, Cp* = pentamethylcyclopentadienyl. The complexes were characterized by relevant analytical techniques (i.e. elemental analysis, FT-IR, NMR, ESI-MS), and their in vitro cytotoxicity was assessed at six cancerous and two non-cancerous (healthy) human cell lines. Overall, complexes 4 – 6 , containing the L2 bridging ligand, revealed higher cytotoxicity as compared with 1 – 3 and, thus, they were studied in greater detail. The best-performing complex 6 exceeded at least twice the in vitro cytotoxicity of cisplatin and showed high selectivity towards the cancer cells over the normal ones, including the primary culture of human hepatocytes. In contrast to cisplatin, complexes 4 – 6 did not induce the cell cycle modification of the treated A2780 human ovarian carcinoma cells (studied by flow cytometry and Western blot analysis). High levels of superoxide anion were induced by complexes 4 – 6 at the A2780 cells. The levels of activated forms of Caspase-3 and Caspase-8 at the A2780 cells treated by Ru(II) complex 4 were comparable with cisplatin, while complexes 5 and 6 had only a minor effect on activation of these caspases.  相似文献   

14.
The title compounds, poly­[bis(2,2′‐bi­pyridine)­bis(μ3‐hydrogen phosphato)­nitratodi‐μ2‐oxo‐dicopper(II)­vanadium dihydrate], [Cu2(VO2)(HPO4)2(NO3)(C10H8N2)2]·2H2O, (I), and poly­[bis(2,2′‐bi­pyridine)­bis(μ3‐hydrogen phosphato)­nitratodi‐μ2‐oxo‐dicopper(II)­vanadium phospho­ric acid solvate], [Cu2(VO2)(HPO4)2(NO3)(C10H8N2)2]·H3PO4, (II), were obtained by similar hydro­thermal methods but under different crystallization conditions. The trinuclear entity which serves as the basic unit in both structures presents two independent CuII ions immersed in similar square‐pyramidal N2O3 environments plus an octahedral VO6 core and is organized into a one‐dimensional polymer, which is essentially identical in the two structures. The compounds are stabilized by different solvates, viz. two crystallization water mol­ecules in (I) and a phospho­ric acid mol­ecule in (II), which provide the main structural differences through the diversity of interchain interactions in which they serve as bridges.  相似文献   

15.
In the complex (morpholine)[2‐hydroxy‐N′‐(5‐nitro‐2‐oxidobenzylidene)benzohydrazidato]nickel(II), [Ni(C14H9N3O5)(C4H9NO)], (I), the NiII center is in a square‐planar N2O2 coordination geometry. The complex bis[μ‐2‐hydroxy‐N′‐(2‐oxidobenzylidene)benzohydrazidato]bis[(morpholine)zinc(II)], [Zn2(C14H10N2O3)2(C4H9NO)2], (II), consists of a neutral centrosymmetric dimer with a coplanar Zn22‐O)2 core. The two ZnII centers are bridged by phenolate O atoms. Each ZnII center exhibits a distorted square‐pyramidal stereochemistry, in which the four in‐plane donors come from the O,N,O′‐tridentate 2‐hydroxy‐N′‐(2‐oxidobenzylidene)benzohydrazidate(2−) ligand and a symmetry‐related phenolate O atom, and the axial position is coordinated to the N atom from the morpholine molecule. There are intramolecular phenol–hydrazide O—H...N hydrogen bonds present in both (I) and (II). In (I), square‐planar nickel complexes are linked by intermolecular morpholine–morpholine N—H...O hydrogen bonds, leading to a one‐dimensional chain, while in (II) an infinite two‐dimensional network is formed via intermolecular hydrogen bonds between the coordinated morpholine NH groups and the uncoordinated phenolate O atoms.  相似文献   

16.
A V-shaped ligand bis(N-methylbenzimidazol-2-ylmethyl)benzylamine (L) and its zinc(II) complex, [ZnL 2](pic)2?·?2CH3CN (pic?=?picrate), have been synthesized and characterized by physico-chemical and spectroscopic methods. Single-crystal X-ray crystallographic analysis revealed that the Zn(II) complex possesses a distorted trigonal bipyramidal geometry. Supramolecular interactions arising from various intra- or intermolecular π···π stacking interactions contributed to the form of the multidimensional configuration. Interactions of L and Zn(II) complex with DNA were monitored using spectrophotometric methods and viscosity measurements. The results suggest that L and Zn(II) complex both bind to DNA via intercalation and Zn(II) complex binds to DNA more strongly than L. Moreover, the Zn(II) complex also exhibited potential antioxidant properties in vitro.  相似文献   

17.
The synthesis and characterization of two pyrazolate‐bridged dicopper(II) complexes, [Cu2(L1)2(H2O)2](ClO4)2 ( 1 , HL1=3,5‐dipyridyl‐4‐(2‐keto‐pyridyl)pyrazole) and [Cu2(L2)2(H2O)2](ClO4)2 ( 2 , HL2=3,5‐dipyridyl‐4‐benzoylpyrazole), are discussed. These copper(II) complexes are formed from the reactions between pyridine‐2‐aldehyde, 2‐acetylpyridine (for compound 1 ) or acetophenone (for compound 2 ), and hydrazine hydrate with copper(II) perchlorate hydrate under ambient conditions. The single‐crystal X‐ray structure of compound 1? 2 H2O establishes the formation of a pyrazole ring from three different carbon centers through C? C bond‐forming reactions, mediated by copper(II) ions. The free pyrazoles (HL1 and HL2) are isolated from their corresponding copper(II) complexes and are characterized by using various analytical and spectroscopic techniques. A mechanism for the pyrazole‐ring synthesis that proceeds through C? C bond‐forming reactions is proposed and supported by theoretical calculations.  相似文献   

18.
Reversed phase liquid chromatography using UV detection was developed for the simultaneous analysis of Hg(II), Pb(II), Cd(II), Ni(II), Fe(III) and V(V) ions after their complexation with pyrrolidine-dithiocarbamate (PDC). Optimum chromatographic conditions were a μ-Bondapak C18 column and an isocratic mobile phase consisting of 40 mmol L?1 SDS, 34 mmol L?1 TBABr and 68% acetonitrile in 10 mmol L?1 phosphate buffer pH 3.5. The separation of six PDC complexes was achieved within 8 min. Analytical performances and method validation were investigated. The detection limits ranged from 0.16 μg L?1(Fe(III)) to 5.40 μg L?1(Pb(II)). Recoveries obtained for all the studied samples including tap water, whole blood and vegetables were 72–98%. The results obtained from the proposed method were not significantly different compared to those obtained from atomic absorption spectrometry (P = 0.05).  相似文献   

19.
Abstract

New copper(II) propionate compounds of composition Cu(prop)2L (L =methyl-3-pyridylcarbamate or N, N-diethylnikotinamide) andau(prop)2L2 (L = methyl-3-pyr-idylcarbamate or2, 6-pyridinemethanole) have been prepared. The crystal and molecular structure of thetetrakis(μ-propionato)di(methyl-3-pyridinecarbamate) dicopper(II), Cu-2(prop)4(mpc)2, was determined by direct method and Fouriertechniques. The compound crystallizes in the orthorhombic space group Pcab with four dimeric units in a cell withdimensions a = 19.350(4), b = 15.390(3), c = 10.725(2)Å. The structure was refined byfull-matrix least-squares methods to a R factor of 0.031, based on 3666 independent reflections. Thecompound is dimeric, with square-pyramidal geometry at each copper centre. The two copper atoms are bridgedby four carboxylate groups, while the apical ligands are methyl-3-pyridylcarbamate. The structural dataare compared with those found in similar copper(II) propionates. Spectral data of Cu(prop)2L aretypical for dimeric copper(II) compounds. Both Cu(prop)2L2 compounds seem to possessoctahedral cop-per(II) stereochemistry with differing tetragonal distortion.  相似文献   

20.
Complexes of nickel(II) aryl carboxylates with a general formula Ni(RC6H4COO)2L2 where R=H, p-CH3. p-Cl, m- & p-NO2; and L = morpholine and piperidine; have been prepared by the interaction of nickel(II) aryl carboxylates with a large excess of appropriate amine. Unlike parent anhydrous nickel(II) aryl carboxylates all these complexes are soluble in common organic solvents.  相似文献   

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