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1.
Reactions of copper salts, zoledronic acid, and 2,2′-bipyridine/1,10-phenanthroline in aqueous ethanolic solutions afforded four phosphonate oxygen-bridged copper complexes, Cu(bipy)(H4zdn)(HSO4) (1), [Cu2(bipy)2(H2zdn)(H2O)(Cl)]·4H2O (2), [Cu2(phen)2(H2zdn)(H2O)(Cl)]·2.5H2O (3), and [Cu3(bipy)3(H4zdn)(H2zdn)(SO4)]·5H2O (4) (H5zdn = zoledronic acid, bipy = 2,2′-bipyridine, phen = 1,10-phenanthroline). The copper centers of 14 have square pyramidal coordination geometries. The Cu(II) ions are coordinated to bipy/phen, zoledronate, and HSO4?/Cl? forming mononuclear units for 1, dinuclear for 2 and 3, and trinuclear for 4. These building units are further extended into 3-D supramolecular networks via multiple hydrogen bond interactions. Temperature-dependent magnetic properties of 2 and 4 suggest weak antiferromagnetic coupling (J = ?4.53(8) cm?1 for 2, J = ?1.69(4) cm?1 for 4). The antitumor activity of 2 was evaluated against the human lung cancer cell line and indicates effective time- and dose-dependent cytotoxic effects.  相似文献   

2.
Three novel heterobinuclear complexes have been prepared and identified as [Cu(oxap)Ni(L)2](ClO4)2·ξH2O, where oxap denotes theN,N′-bis(2-aminopropyl)oxamido dianion and L denotes 2,2′-bipyridine (bipy), 1,10-phenanthroline (phen) or 5-nitro-1,10-phenanthroline (NO2-phen). The crystal structure of [Cu(oxap)Ni(phen)2]-(ClO4)2·2H2O has been determined. Crystal data: triclinic, space group , a=12.079 (6), b=12.409 (4), c=17.261 (8) ?, α=70.91 (2), β=86.72 (4), γ=89.19 (3)o. At room temperature, Z=2. The CuII is in a square planar environment and the NiII is in an octahedral environment. The Cu−Ni distance is 5.292 ?. The temperature dependences of the magnetic susceptibilities of [Cu(oxap)Ni(phen)2]-(ClO4)2·2H2O and [Cu(oxap)Ni(bipy)2](ClO4)2 have been studied in the 4.2–300 K range, giving the exchange integral J=−92.4 cm−1 for bipy and J=−94.3 cm−1 for phen. These results are commensurate with antiferromagnetic interactions between the adjacent metal ions.  相似文献   

3.
Three new Ru(II) complexes, [Ru(dmb)2(ipad)](ClO4)2 (dmb = 4,4′-dimethyl-2,2′-bipyridine, ipad = 2-(anthracene-9,10-dione-2-yl) imidazo[4,5-f][1,10]phenanthroline, 1), [Ru(dmp)2(ipad)](ClO4)2 (dmp = 2,9-dimethyl-1,10-phenanthroline, 2), and [Ru(dip)2(ipad)](ClO4)2 (dip = 4,7-diphenyl-1,10-phenanthroline, 3), have been synthesized and characterized. The three Ru(II) complexes intercalate with the base pairs of DNA. The in vitro antiproliferative activities and apoptosis-inducing characteristics of these complexes were investigated. The complexes exhibited cytotoxicity against various human cancer cell lines. BEL-7402 cells displayed the highest sensitivity to 1, accounted for by the greatest cellular uptake. Complex 1 was shown to accumulate preferentially in the nuclei of BEL-7402 cells and cause DNA damage and induce apoptosis, which involved cell cycle arrest and reactive oxygen species generation.  相似文献   

4.
Three ternary copper(II) complexes [Cu(L1)(phen)] (1), [Cu(L2)(phen)] (2), and [Cu(L3)(phen)]·2H2O (3) (L1 = 4-fluoro-2-(picolinamido)benzoic acid, L2 = 4,5-difluoro-2-(picolinamido)benzoic acid, L3 = 4,5-difluoro-2-((2-hydroxybenzylidene)amino)benzoic acid, phen = 1,10-phenanthroline) have been synthesized and characterized by physicochemical and spectroscopic methods. In addition, X-ray crystallography showed that the Cu atoms in each of the complexes are five-coordinate, adopting distorted square pyramidal or trigonal bipyramidal geometries. The interactions of the complexes with calf-thymus DNA were investigated by UV absorption, fluorescence spectroscopy and viscosity measurements. In addition, the complexes were screened for in vitro cytotoxicity against A549 (human pulmonary carcinoma cells), Jurkat (human T lymphocyte cell line) and HepG-2 (human liver hepatocellular carcinoma cells); these experiments showed that complex 3 exhibited the most effective cytotoxicities (IC50 = 1.224–7.099 µM). Antibacterial studies revealed that complex 3 also exhibited highest activity, consistent with the DNA binding affinities.  相似文献   

5.
Two coordination complexes, namely [Co(phen)(H2O)L]·H2O and [Ni2(phen)2(H2O)2L2]·4H2O (phen = 1,10-phenanthroline, H2L = 1,3-adamantanedicarboxylic acid) have been hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction. [Co(phen)(H2O)L]·H2O consists of 1D chains of the complex plus lattice H2O molecules. Interchain hydrogen bonds and π–π stacking interactions assemble the 1D chains into 2D layers. [Ni2(phen)2(H2O)2L2]·4H2O is a binuclear complex which is assembled into a 3D supramolecular structure by strong hydrogen bonds and π–π stacking interactions. Both complexes were characterized by physico-chemical and spectroscopic methods.  相似文献   

6.
Six new coordination complexes, Ln2(2,2′-oba)2(phen)2(ox)(H2O)2 (Ln = Eu 1, Tb 2), Ln4(2,2′-oba)6(phen)2 (Ln = Eu 3, Tb 4), Eu4(2,2′-oba)6(phen)2(H2O) (5), and K[Eu(2,2′-oba)2(phen)2] (6) [2,2′-H2oba = 2,2′-oxybis(benzoic acid), phen = 1,10-phenanthroline, H2ox = oxalic acid] were synthesized by hydrothermal reactions with the same compound molar ratios but different modulatory reagents (MRs). Complexes 1–5 have different 1-D chain structures and 6 shows a mononuclear structure. These complexes form diverse 3-D supramolecular networks through hydrogen bonds. The interaction between these complexes and hippuric acid (HA) or bovine serum albumin (BSA) was investigated by fluorescence spectral analysis. Interestingly, the hippuric acid could quench the luminescence of these complexes while the fluorescence of BSA could be quenched by these complexes. Results suggested that the complexes may be potential luminescent testing reagents for HA or BSA by significant fluorescence quenching of Ln3+ or BSA, respectively, through a static and dynamic quenching process.  相似文献   

7.
Two polypyridyl ligands 6-fluro-3-(1H-imidazo [4,5-f] [1,10]-phenanthroline-2-yl)-4H-chromen-4-one (FIPC), 6-chloro-3-(1H-imidazo [4,5-f] [1,10]-phenanthroline-2-yl)-4H-chromen-4-one (ClIPC) polypyridyl ligands and their Ru(II) complexes [Ru(bipy)2FIPC]2+(1), [Ru(dmb)2FIPC]2+(2), [Ru(phen)2FIPC]2+(3), [Ru(bipy)2ClIPC]2+(4), [Ru(dmb)2ClIPC]2+(5) and [Ru(phen)2ClIPC]2+(6) ((bipy = 2,2′-bipyridine, dmb = 4,4′-dimethyl-2,2′-bipyridine and phen = 1,10-phenanthroline) have been synthesised and characterised by elemental analysis, Mass spectra, IR, 1H and 13C-NMR. The DNA-binding of the six complexes to calf-thymus DNA (CT-DNA) has been investigated by different spectrophotometric, fluorescence and viscosity measurements. The results suggest that 1–6 complexes bind to CT-DNA through intercalation. The variation in binding affinities of these complexes is rationalised by a consideration of electrostatic, steric factors and nature of ancillary ligands. Under irradiation at 365 nm, the three complexes have also been found to promote the photocleavage of plasmid pBR 322 DNA. Inhibitor studies suggest that singlet oxygen (1O2) plays a significant role in the cleavage mechanism of Ru(II) complexes. Thereby, under comparable experimental conditions [Ru(phen)2FIPC]2+(3), [Ru(phen)2ClIPC]2+(6) cleaves DNA more effectively than 1, 2, 4 and 5 complexes do. The Ru(II) polypyridyl complexes (1–6) have been screened for antimicrobial activities.  相似文献   

8.

Two novel manganese(II) complexes, [Mn(phen)2N3·H2O]ClO4·H2O and Mn(phen)2(N3)2 have been synthesized by the reaction of Mn(ClO4)2·6H2O and Mn(CH3CO2)2·4H2O with NaN3 and phen in EtOH/H2O solution, respectively (where phen = 1,10-phenanthroline). Their crystal structures have been determined by X-ray diffraction. Both complex molecules have distorted octahedral geometry and two 1,10-phenanthroline molecules chelate to a Mn(II) atom with a cis-configuration. To [Mn(phen)2N3·H2O]ClO4·H2O, one nitrogen atom from an azide anion and one oxygen atom from a water molecule cis-coordinate to the Mn(II) atom while two nitrogen atoms occupy cis positions in Mn(phen)2(N3)2. These complexes are versatile precursors for the design of heteropolymetallic systems.  相似文献   

9.
Platinum(II) complexes, [Pt(Lx)X2] (16), where X = Br or I and Lx = 2,2′-bipyridine or 1,10-phenanthroline derivatives (5,5′-dimethyl-2,2′-bipyridine (5-Mebpy), 4,4′-dimethyl-2,2′-bipyridine (4-Mebpy), and 5-amino-1,10-phenanthroline (5-NH2phen)) were prepared. The complexes were characterized by the elemental analysis, mass spectrometry, infrared, and multinuclear (1H, 13C and 195Pt) 1-D and 2-D NMR spectroscopies, and by single-crystal X-ray analysis of [Pt(4-Mebpy)I2] (4). All the platinum(II) complexes (16) were evaluated for in vitro cytotoxicity against human cancer cell lines A2780 and A2780R, and against non-malignant MRC5 cell line. All the complexes were nontoxic up to the 50 μM concentration, although they were found to readily bind to calf-thymus DNA (CT-DNA), as determined by spectrophotometric titration (Kb ≈ 107 M?1) and ethidium bromide displacement assay.  相似文献   

10.
In the present study three new imidazole derivatives of phen, 2-(4-hydroxy-3,5-diiodophenyl) imidazo[4,5-f][1,10]phenanthroline L1, 2-(2-hydroxy-3,5-diiodophenyl)imidazo[4,5-f][1,10]phenanthroline L2, 2-(4-hydroxy-5-iodo-3-methoxyphenyl)imidazo[4,5-f][1,10]phenanthroline L3 and their nine new polypyridine complexes[M(N–N)2(L1–3)](OAc)2·(nH2O) where M is Ni(II), Co(II) and Cu(II) and where (N–N)2 is 2,2′-bipyridine (bpy)2 or 1,10-phenanthroline (phen)2 have been synthesized from the reaction of the metal precursor complexes [M(phen)2(OAc)2]·(nH2O) and [M(bpy)2(OAc)2]·(nH2O) with the respective ligands in ethanol and water. The structures of the compounds were determined with the aid of elemental analysis and FT-IR, UV–Vis, 1H NMR, ESR spectroscopic methods, magnetic measurements and conductance measurements, further analyzed by powder XRD and thermal studies. Elemental analysis data suggested that the complexes have a 1:2:1 molar ratio among the metal and phen or bpy and L1/L2 or L3 ligands. The spectral data show that all the complexes were six coordinated and possess octahedral geometry around the metal ions. The X-band ESR spectrum of the Cu(II) in DMSO solution at room temperature was recorded and observed anisotropic g values indicate the presence of metal ion in an octahedral environment. The powder XRD patterns of complexes recorded in the range (2θ = 0–80°) and average crystallite size (dXRD) was calculated using Scherrer’s formula. Thermal decomposition profiles of complexes show high decompound temperatures indicating a good thermal stability. Binding of the complexes with calf thymus DNA (CT DNA) has been investigated by gel electrophoresis. The experimental results indicate that the complexes bind to DNA by intercalation mode and found to promote cleavage of plasmid pBR 322 DNA from the supercoiled form I to the open circular form II upon irradiation.  相似文献   

11.
《Journal of Coordination Chemistry》2012,65(17-18):1577-1585
Two 2D complexes, [Co(mal)(phen)(H2O)2] (1) and [Ni(mal)(phen)(H2O)2] (2) (mal?=?malonate dianion; phen?=?1,10-phenanthroline), have been synthesized by the reaction of Co(ClO4)2·6H2O and Ni(ClO4)2·6H2O with disodium malonate and 1,10-phenanthroline in MeOH/H2O solution. Their crystal structures have been determined by X-ray diffraction. The structures of Complexes 1 and 2 show that each metal ion is coordinated by one 1,10-phenanthroline, two water molecules and a malonate ligand forming a distorted octahedral environment and each mononuclear fragment forms a 2D supramolecular network through H-bonding interactions.  相似文献   

12.
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   

13.
Six new μ-terephthalato iron(III) binuclear complexes have been prepared and identified: [Fe2(TPHA)(L)4]-(ClO4)4 [L = 2,2′-bipyridine (bpy); 1,10-phenanthroline (phen); 4,4′-dimethyl-2,2′-bipyridine (Me2bpy); 5-methyl-1,10-phenanthroline (Me-phen); 5-chloro-1,10-phenanthroline (Cl-phen) and 5-nitro-1,10-phenanthroline (NO2-phen)]; where TPHA = the terephthalate dianion. Based on the elemental analyses, molar conductance and magnetic moments of room-temperature measurements, and spectroscopic studies, extended TPHA-bridged structures consisting of two iron(III) ions, each in an octahedral environment, are proposed for these complexes. The [Fe2(TPHA)(Me-phen)4](ClO4)4 (1) and [Fe2(TPHA)(phen)4](ClO4)4 (2) complexes were characterized by variable temperature magnetic susceptibility (4–300 K) measurements and the observed data were successfully simulated by the equation based on the spin Hamiltonian operator, Ĥ = −2 1 Ŝ 2, giving the exchange integrals J = −1.05 cm−1 for (1) and J = −9.28 cm−1 for (2). This result indicates the presence of a weak antiferromagnetic spin-exchange interaction between the metal ions within each molecule. The influence of the terminal ligand methyl substituents on magnetic interactions between the metals is also discussed. This revised version was published online in June 2006 with corrections to the Cover Date.  相似文献   

14.
含二茂铁基的锌配合物的结构及其生物活性   总被引:1,自引:0,他引:1  
合成了4个含二茂铁基的锌配合物[Zn(FcCOO)(phen)2]ClO4·FcCOOH (1)(FcCOO=二茂铁甲酸根,phen=1,10-邻菲咯啉),[Zn(FcCOO)(phen)2]·ClO4·H2O (2),[Zn(FcCOO)(FcCOGly)(phen)]·C2H5OH (3)(FcCOGly=二茂铁甲酰化甘氨酸)和[Zn(FcCOGly)2(phen)]·CH3OH (4)。用X-射线单晶衍射测定了配合物的晶体结构。对4个配合物的生物活性进行了初步研究,发现配合物的抗菌活性与配合物的配位键强度及phen含量有一定的关系。  相似文献   

15.
Four linear trinuclear transition metal complexes have been prepared and characterized. The complexes [MII(MeOH)4][FeIII(L)2]2·2MeOH (M = Fe (1) or Ni (2)), [CoII(EtOH)2(H2O)2][FeIII(L)2]2·2EtOH (3), and [MnII(phen)2][MnIII(L)2]2·4MeOH (4) (H2L = ((2-carboxyphenyl)azo)-benzaldoxime, phen = 1,10-phenanthroline) possesses a similar synanti carboxylate-bridged structure. The terminal Fe(III) or Mn(III) ions are low spin, and the central M(II) ions are high spin. Magnetic measurements show that antiferromagnetic interactions were present between the adjacent metal ions via the synanti carboxylate bridges. The antiferromagnetic coupling between low-spin Fe(III) and Ni(II) is unusual, which has been tentatively assigned to the structural distortion of Fe(III).  相似文献   

16.
Four coordination complexes of copper(II) and iron(II), namely [CuCl(phen)2](5-NO2-Hipa)·2H2O (BUC-10), [Cu(phen)(3,4-H2dczpb)(H2O)]·H2O (BUC-11), [Fe(phen)(L)(H2O)]2 (BUC-12), and [Fe(phen)3](3,4-H3dczpb)2·0.6H2O (BUC-13) (phen = 1,10-phenanthroline; 5-NO2-H2ipa = 5-nitroisophthalic acid; 3,4-H4dczpb = 3,4-dicarboxyl-(3′,4′-dicarboxylazophenyl) benzene; L = 6,12-dihydroxy-1,2,6,12-tetrahydroindazolo[2,1-a]indazole-1,7-dicarboxylic acid), have been synthesized under hydrothermal conditions. All four complexes were characterized by single-crystal X-ray diffraction, FTIR, elemental analysis and UV–Vis diffuse reflection spectroscopy. The photocatalytic performances of the complexes for decomposition of methylene blue under UV irradiation were also investigated.  相似文献   

17.
Summary Four new trinuclear copper(II) complexes, [Cu(phen)-(NBzIm)] (ClO4) (1), [Cu(bpy)(NBzIm)](ClO4) (2), [Cu-(Me2-bpy)(NBzIm)](Ac)·1/2H2O (3) and [Cu(Me2-bpy)-(Im)](ClO4)·1/2H2O (4) (phen = 1, 10-phenanthroline, bpy = 2,2-bipyridine, NBzIm = 6-nitrobenzimidazolate ion, Im=imidazolate ion) have been prepared and characterized by variable temperature magnetic susceptibility measurements. A weak antiferromagnetic spin exchange interaction operates between copper(II) ions, exchange integrals evaluated as J =-23.82 cm-1 for (1); and J=-21.91 cm-1 for (2).  相似文献   

18.
A new benzimidazoyl ligand bis[(N-ethylbenzimidazol-2-yl)methyl]ether (EDGB) and CuII complexes [Cu(L1) (L2)](ClO4)·mEt2O·nH2O [L1 = bis[(benzimidazol-2-yl)methyl]ether (DGB) or EDGB, L2 = 2,2-bipyridine (bipy) or 1,10-phenanthroline (phen)] have been synthesized and characterized by elemental analyses and i.r. spectra. The single-crystal structure of the [Cu(phen)(DGB)(OClO3)]ClO4·Et2O·0.5H2O complex was determined by X-ray diffraction. The geometry around Cu is best described as a distorted octahedron with four nitrogen atoms from phen and DGB ligands forming the equatorial plane. The oxygen atoms of DGB and one perchlorate group are in the axial positions with semi-coordinated bonding modes. The electrochemical behavior of the complexes is described.  相似文献   

19.
Three ternary copper(II) complexes, [Cu(phen)(L-phe)Cl]·2H2O, [Cu(phen)(L-leu)Cl]·4½H2O, and [Cu(phen)(L-tyr)Cl]·3H2O, and four binary copper(II) complexes, [Cu(phen)Cl2], Cu(L-phe)2·½H2O, Cu(L-leu)2·½H2O, and Cu(L-tyr)2·H2O (where phen = 110-phenanthroline, L-phe = L-phenylalanine, L-tyr = L-tyrosine, L-leu = L-leucine and Cl- = chloride), were synthesized and characterized by elemental analysis, spectroscopic techniques (FTIR, UV–visible, fluorescence spectroscopy), magnetic susceptibility, molar conductivity, and lipophilicity measurement. X-ray diffraction determination of a single crystal of [Cu(phen)(L-tyr)Cl] showed two independent molecules in the asymmetric unit, each with the same distorted square pyramidal geometry about copper(II). p-Nitrosodimethylaniline assay revealed that the three ternary complexes were better inducers of reactive oxygen species over time than binary complexes, CuCl2, and free ligands. All the copper(II) complexes in this series inhibited the three proteolytic activities in the order Trypsin-like > Caspase-like > Chymotrypsin-like. In terms of anticancer properties, the copper(II)-phen complexes had GI50 values of less than 4 μM against MCF-7, HepG2, CNE1 and A549 cancer cell lines, more potent than cisplatin.  相似文献   

20.
Two complexes, [CuII(L1)(phen)2](ClO4) (1) and [NiII2(L1)2(phen)2(MeOH)2](ClO4)2 (2), with HL1, a ligand derived from protocatechuic acid (=2,3-dihydrobenzo[b][1,4]dioxine-6-carboxylic acid) and phen (=1,10-phenanthroline) were synthesized and characterized by C, H, and N elemental analysis, UV–vis, FT-IR, and single-crystal X-ray diffraction, which revealed that 1 is mononuclear and 2 is dinuclear. Both complexes crystallized in monoclinic space group C2/c. The urease inhibitory activity and in vitro cytotoxic activity of 1 and 2 were tested. The complexes showed strong inhibitory activity against jack bean urease and significantly suppressed the growth of A549, L929, and SW620 cell lines.  相似文献   

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