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1.
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
2.
Qing-Jun Niu Jeff X. Zhou Hong-Lin Zhu Qing Huang Wei Xu 《Journal of Coordination Chemistry》2016,69(9):1447-1462
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 1–4 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
3.
《Journal of Coordination Chemistry》2012,65(4):699-714
(E)-2-(2-hydroxybenzylideneamino)isoindoline-1,3-dione (Hbid) was prepared by condensation of N-aminophthalimide and salicylaldehyde and characterized by elemental analysis, IR, 1H-NMR, and mass spectral studies. Mononuclear complexes [(phen)CuII(μ-Hbid)2H2O] (1), [(phen)CoII(Cl)2(μ-Hbid)]6H2O (2) (phen?=?1,10-phenanthroline) and binuclear complexes [CuII(μ-Hbid)]2 (3), and [CoII(μ-Hbid)]2 (4) with Hbid were prepared and characterized by elemental analysis, IR, UV-Vis, molar conductance, and thermogravimetric (TG) techniques. DNA-binding properties of 1–4 were investigated by UV spectroscopy, fluorescence spectroscopy, and viscosity measurements. The results suggest that 1 and 2 bind to DNA by partial intercalation, whereas 3 and 4 find different groove-binding sites. The cleavage of these complexes with super coiled pUC19 has been studied using gel electrophoresis; all the complexes displayed chemical nuclease activity in the absence and presence of H2O2 via an oxidative mechanism. Complexes 1–4 inhibit the growth of both Gram-positive and Gram-negative bacteria. 相似文献
4.
Synthesis,Structure, and Luminescent Properties of Lanthanide Coordination Polymers Based on 5‐Hydroxyisophthalate and Phen Ligands
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Three lanthanide coordination polymers incorporating 5‐hydroxyisophthalate ( L ) and phen ligands, [Eu( L )(phen)]n ( 1 ) and [Ln( L )(phen)2]n [Ln = Sm ( 2 ) and Pr ( 3 )], were synthesized. X‐ray structural analysis reveals that 1 features a (3,6)‐connected 3D rtl topology. Complexes 2 and 3 are isostructural and have 2D sheets with 63 topology. Comparison of the structural differences between 1 and 2 (or 3 ) suggests that the different metal sources play an important role in the formation of such coordination networks. Compounds 1 and 2 show photoluminescence and their emission properties are closely related to their corresponding central LnIII atoms. 相似文献
5.
Heterotrimetallic Coordination Polymers: {CuIILnIIIFeIII} Chains and {NiIILnIIIFeIII} Layers: Synthesis,Crystal Structures,and Magnetic Properties
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Dr. Maria‐Gabriela Alexandru Dr. Diana Visinescu Prof. Marius Andruh Dr. Nadia Marino Dr. Donatella Armentano Dr. Joan Cano Prof. Francesc Lloret Prof. Miguel Julve 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(14):5429-5446
The use of the [FeIII(AA)(CN)4]? complex anion as metalloligand towards the preformed [CuII(valpn)LnIII]3+ or [NiII(valpn)LnIII]3+ heterometallic complex cations (AA=2,2′‐bipyridine (bipy) and 1,10‐phenathroline (phen); H2valpn=1,3‐propanediyl‐bis(2‐iminomethylene‐6‐methoxyphenol)) allowed the preparation of two families of heterotrimetallic complexes: three isostructural 1D coordination polymers of general formula {[CuII(valpn)LnIII(H2O)3(μ‐NC)2FeIII(phen)(CN)2 {(μ‐NC)FeIII(phen)(CN)3}]NO3 ? 7 H2O}n (Ln=Gd ( 1 ), Tb ( 2 ), and Dy ( 3 )) and the trinuclear complex [CuII(valpn)LaIII(OH2)3(O2NO)(μ‐NC)FeIII(phen)(CN)3] ? NO3 ? H2O ? CH3CN ( 4 ) were obtained with the [CuII(valpn)LnIII]3+ assembling unit, whereas three isostructural heterotrimetallic 2D networks, {[NiII(valpn)LnIII(ONO2)2(H2O)(μ‐NC)3FeIII(bipy)(CN)] ? 2 H2O ? 2 CH3CN}n (Ln=Gd ( 5 ), Tb ( 6 ), and Dy ( 7 )) resulted with the related [NiII(valpn)LnIII]3+ precursor. The crystal structure of compound 4 consists of discrete heterotrimetallic complex cations, [CuII(valpn)LaIII(OH2)3(O2NO)(μ‐NC)FeIII(phen)(CN)3]+, nitrate counterions, and non‐coordinate water and acetonitrile molecules. The heteroleptic {FeIII(bipy)(CN)4} moiety in 5 – 7 acts as a tris‐monodentate ligand towards three {NiII(valpn)LnIII} binuclear nodes leading to heterotrimetallic 2D networks. The ferromagnetic interaction through the diphenoxo bridge in the CuII?LnIII ( 1 – 3 ) and NiII?LnIII ( 5 – 7 ) units, as well as through the single cyanide bridge between the FeIII and either NiII ( 5 – 7 ) or CuII ( 4 ) account for the overall ferromagnetic behavior observed in 1 – 7 . DFT‐type calculations were performed to substantiate the magnetic interactions in 1 , 4 , and 5 . Interestingly, compound 6 exhibits slow relaxation of the magnetization with maxima of the out‐of‐phase ac signals below 4.0 K in the lack of a dc field, the values of the pre‐exponential factor (τo) and energy barrier (Ea) through the Arrhenius equation being 2.0×10?12 s and 29.1 cm?1, respectively. In the case of 7 , the ferromagnetic interactions through the double phenoxo (NiII–DyIII) and single cyanide (FeIII–NiII) pathways are masked by the depopulation of the Stark levels of the DyIII ion, this feature most likely accounting for the continuous decrease of χM T upon cooling observed for this last compound. 相似文献
6.
《Journal of Coordination Chemistry》2012,65(3):424-430
Four 2-D coordination polymers Ln2(phen)2(C5H6O4)3 [Ln?=?Pr(1), Eu(2), Er(3), Yb(4), phen?=?1,10-phenanthroline] were obtained via hydrothermal reactions and determined by X-ray diffraction analysis. The crystal structure data reveal that these complexes are isostructural. In the asymmetric unit, the two Ln(III) ions are nine-coordinate and have similar coordination environments. The Ln(III) ions are built into 2-D layers by three different coordination modes of glutarate. The resulting 2-D layer forms 3-D supramolecular architecture by two types of π···π stacking interactions. All the complexes were characterized by IR spectra and thermogravimetric analysis, and the emission spectrum shows that Eu2(phen)2(C5H6O4)3 possesses strong luminescence. 相似文献
7.
由水热法合成了2个微孔镧系超分子配合物[Ln(CCA)(OH)(phen)(H2O)]n·n(phen)·nH2O(Ln=Yb,1;Er,2;H2CCA=2-羧基肉桂酸;phen=1,10-菲啰啉),并用元素分析、IR及X-射线单晶衍射对其进行了表征。晶体结构研究表明,2个配合物都是由配体2-羧基肉桂酸连接而形成的一维双链结构,该链状结构通过氢键和π-π堆积作用扩展为具有微孔结构的超分子。1,10-菲啰啉在微孔结构的形成过程中起到了模板剂的作用。 相似文献
8.
《Journal of Coordination Chemistry》2012,65(8):1412-1422
A family of phenoxo-bridged heterometallic Schiff base trinuclear complexes, [Fe2LnL2(C3H7COO)(H2O)]·CH3OH·CH3CN·H2O (Ln = Sm, 1; Gd, 2; Tb, 3; Dy, 4) is reported. Those complexes were afforded by “one-pot” reaction of a polydentate Schiff base ligand 2-hydroxy-3-methoxy-phenylsalicylaldimine (H2L) with Fe(NO3)3·9H2O, Ln(NO3)3·6H2O and sodium butyrate (C3H7COONa) in a mixture of methanol and acetonitrile in the presence of triethylamine as a base. Single-crystal X-ray diffraction analysis reveals that the structures of the four complexes are isomorphic. In each complex, two anionic [FeL2]? units coordinate to the central lanthanide ion as a tetradentate ligand using its four phenoxo oxygens, forming a two-blade propeller-like molecular shape. Magnetic properties of 1–4 were investigated using variable temperature magnetic susceptibility, and weak ferromagnetic exchange between the FeIII and LnIII ions has been established for the Gd derivative. The Tb and Dy complexes show no evidence of slow relaxation behavior above 2.0 K. 相似文献
9.
《Journal of Coordination Chemistry》2012,65(4):583-592
Two complexes [Ln2(hfga)2(phen)4(H2O)6] · hfga · 2H2O (H2hfga = hexafluoroglutaric acid, phen = 1, 10-phenanthroline, Ln=Tb, 1; Eu, 2) were synthesized under hydrothermal conditions and their structures determined by X-ray crystallography. The complexes consist of dinuclear units with an inversion center. Each Ln(III) is nine-coordinate with two carboxylate oxygens from two hfga ligands, three oxygens from water and four nitrogens from two phen molecules. Two carboxylate groups of one hfga adopt monodentate coordination to Ln(III) as a long bidentate bridge linking two Ln(III) ions to form a dimer. Ln(III) ··· Ln(III) distances of 9.027(3) Å for 1 and 9.043(3) Å for 2 were observed. Both complexes emit strong fluorescence and show characteristic emission of Tb(III) and Eu(III) ions, respectively. 相似文献
10.
Reactions of phenanthroline (phen) and Er(NO3)3 · 5 H2O or Lu(NO3)3 · H2O in CH3OH/H2O yield [Ln2(phen)4(H2O)4(OH)2](NO3)4(phen)2 with Ln = Er ( 1 ), Lu ( 2 ). Both isostructural complex compounds crystallize in the triclinic space group P 1 (no. 2) with the cell dimensions: a = 11.257(2) Å, b = 11.467(2) Å, c = 14.069(2) Å, α = 93.93(2)°, β = 98.18(1)°, γ = 108.14(1)°, V = 1696.0(6) Å3, Z = 1 for ( 1 ) and a = 11.251(1) Å, b = 11.476(1) Å, c = 14.019(1) Å, α = 93.83(1)°, β = 98.27(1)°, γ = 108.27(1)°, V = 1689.0(3) Å3, Z = 1 for ( 2 ). The crystal structures consist of the hydroxo bridged dinuclear [Ln2(phen)4(H2O)4(OH)2]4+ complex cations, hydrogen bonded NO3– anions and π‐π stacking (phen)2 dimers. The rare earth metal atoms are coordinated by four N atoms of two phen ligands and four O atoms of two H2O molecules and two μ‐OH groups to complete tetragonal antiprisms. Via two common μ‐OH groups, two neighboring tetragonal antiprisms are condensed to a centrosymmetric dinuclear [Ln2(phen)4(H2O)4(OH)2]4+ complex cation. Based on π‐π stacking interactions and hydrogen bonding, the complex cations and (phen)2 dimers form 2 D layers parallel to (1 0 1), between which the hydrogen bonded NO3– anions are sandwiched. The structures can be simplified into a distorted CsCl structure when {[Ln2(phen)4(H2O)4(OH)2](NO3)4} and (phen)2 are viewed as building units. 相似文献
11.
《Journal of Coordination Chemistry》2012,65(21):3829-3838
A series of LnIII–SrII heterometallic coordination polymers formulated as [Ln2Sr3(pda)6(H2O)18]·nH2O (Ln = Pr-1, n = 14; Nd-2, n = 12; Sm-3, n = 11; Eu-4, n = 11; Gd-5, n = 16; Tb-6, n = 13; Dy-7, n = 13) were synthesized via assembly of Ln(NO3)3·6H2O, SrCl2·6H2O, pyridine-2,6-dicarboxylic acid (H2pda) and imidazole (im) in H2O/C2H5OH solution. Single crystal X-ray diffraction revealed that they are isostructural. All of these complexes possess ladder-shaped 1-D chain structures. The luminescent properties of Sm-3, Eu-4, Gd-5, Tb-6 and Dy-7 have been investigated. The solid-state quantum yields and the lifetimes of Eu-4 and Tb-6 are also studied. 相似文献
12.
Changkun Xia Yuanyuan Min Wen Sun Kai Yang Yunlong Wu 《Journal of Coordination Chemistry》2018,71(1):12-21
Two dinuclear Fe(III) metal–organic complexes with tetracarboxylate and chelating N-donor ligands, [Fe(Hbtec)(phen)(H2O)]2·2H2O (1) and [Fe(Hbtec)(bpy)(H2O)]2·2H2O (2) (H4btec = 1,2,3,5-benzenetetracarboxylic acid, phen = 1,10-phenanthroline, bpy = 2,2′-bipyridine) have been prepared and characterized by elemental analysis, IR spectroscopic, and X-ray diffraction methods. Both complexes crystallize in the monoclinic space group P21/c with two Fe(III) ions bridged by two Hbtec3? ligands into a dinuclear unit. Hydrogen bonding connects the dinuclear units into a 3-D framework. The dinuclear units are 10-connected nodes that produce a 3-D framework with topology Schläfli symbol as (312·428·55). Thermal stabilities and luminescent properties of the two complexes have also been investigated. 相似文献
13.
Syntheses,Crystal Structures,and Photophysical Properties of Heteronuclear Zinc(II)/Cadmium(II)‐Lanthanide(III) Coordination Complexes based on Benzoic Acid
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Yu‐Xian Chi Yu‐Qian Liu Xiao‐Shuang Hu Xiao‐Yun Tang Yu‐Juan Liu Jing Jin Shu‐Yun Niu Guang‐Ning Zhang 《无机化学与普通化学杂志》2016,642(1):73-80
The heteronuclear d‐f coordination complexes [Er2Zn2(C6H5COO)10(phen)2] (1), [Ho2Zn2(C6H5COO)10(phen)2] ( 2 ), [Pr3Zn6(C6H5COO)21(phen)3] ( 3 ), [ErCd(C6H5COO)5(phen)·H2O] ( 4 ), [Ho2Cd3(C6H5COO)12(phen)2] ( 5 ), [EuCd2(C6H5COO)7(phen)2] ( 6 ) (C6H5COOH = benzoic acid;phen = 1,10‐phenanthroline) were synthesized by hydrothermal methods, and their structures were studied by single‐crystal X‐ray diffraction. Complexes 1 , 2 , 4 , and 5 crystallize in the triclinic space group P$\bar{1}$ and complexes 3 and 6 in the monoclinic space group C2/c. The room temperature IR, UV/Vis/NIR absorption, and emission spectra of the six complexes were determined and assigned. In the visible and NIR regions, the emission spectra of complexes show characteristic bands of corresponding LnIII ions, which are attributed to the sensitization from the d block (Zn/Cd‐ligand section) and ligands. In comparison with isolated LnIII ions, the NIR emission bands of complexes 1 – 5 exhibit shifting, broadening and splitting, which are also present in their UV/Vis/NIR absorption spectra. Thus, the two spectra of complexes can evidence each other. 相似文献
14.
Syntheses,structures, thermal stabilities and bacteriostatic activities of four lanthanide complexes
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
15.
《Journal of Coordination Chemistry》2012,65(7):1290-1308
Five zinc(II) complexes, [Zn(L1)2] (1), [Zn(L1)2(phen)H2O]·H2O (2), [Zn(L1)2(bipy)] (3), [Zn(L2)2] (4), and [Zn(L2)2(phen)] (5) (where L1?=?4-nitrophenylacetate, L2?=?phenylacetate, phen?=?1,10-phenanthroline and bipy?=?2,2′-bipyridine), have been synthesized and characterized by elemental analysis, FT-IR, and multinuclear NMR. Complexes 2, 3, and 4 have been confirmed by single-crystal X-ray diffraction. In 2 and 3, zinc is bonded monodentate to two carboxylates exhibiting distorted trigonal bipyramidal and tetrahedral geometries, respectively, whereas in 4, the carboxylates are bridging bidentate in distorted tetrahedral geometry. The complexes have been screened for electro- and biological activities, including DNA interaction and enzyme inhibition studies. The effect of concentration of 1–5 on the activity of enzyme, alkaline phosphatase, showed that an increase in concentration of complex decreased the activity of the enzyme. Electrochemical behavior of HL1, 2, and 3 was investigated by cyclic voltammetry and it was observed that ligand-centered electro-activity exhibits a proportionate change on complexation. The UV–visible spectroscopic and viscometric data indicate electrostatic and groove binding of the complexes with DNA. The binding constant and Gibb’s free energy values indicate the feasibility of the complex–DNA interaction and show potent biological activity of the complexes. 相似文献
16.
《Journal of Coordination Chemistry》2012,65(20):3245-3252
Two new complexes, [Co2(CH2=C(CH3)CO2)4(phen)2(H2O)2] (1) and [Pb2(CH2=C(CH3)CO2)4(phen)2] (phen = 1,10-phenanthroline) (2), have been synthesized and structurally characterized by single crystal X-ray diffraction methods. There are two cocrystallized conformers of [Co(CH2=C(CH3)CO2)2(phen)(H2O)] in the asymmetric unit of 1 with the Co atoms displaying similar coordination modes. In the asymmetric unit of 2, there exist two crystallographically independent [Pb(CH2=C(CH3)CO2)2(phen)] molecules with the Pb atoms showing completely different coordination geometries. Weak intermolecular interactions such as hydrogen bonding and π–π stacking are responsible for the supramolecular assembly and stabilization of the crystal structures of 1 and 2. The complexes are characterized by elemental analysis, IR spectra, and UV–Vis spectra. The fluorescent properties of 2 are also discussed. 相似文献
17.
《Journal of Coordination Chemistry》2012,65(21):3868-3876
By controlling the concentration of the reaction system, two zinc(II) complexes, [Zn2(tsgluO)2(phen)2]n (1) and [Zn2(tsgluO)2(phen)2(H2O)2] (2) (H2tsgluO = N-tosyl-L-glutamic acid, phen = 1,10-phenanthroline), have been synthesized under hydrothermal conditions and characterized by elemental analysis, infrared spectra, thermogravimetric analysis, and single-crystal X-ray diffraction. Complexes 1 and 2 both crystallize in the triclinic space group P-1. Complex 1 exhibits a 1-D double-chain structure. Complex 2 has a dinuclear structure which is extended by hydrogen-bonding interactions to form a 2-D supramolecular network. The structural difference indicates that the concentration plays a crucial role in modulating structures of coordination complexes. The two compounds also show intense fluorescence at room temperature. 相似文献
18.
《Journal of Coordination Chemistry》2012,65(24):4040-4046
Two mixed-ligand Cu(II) complexes, [CuL1(Himdz] · CH3OH (1) and [CuL2(phen)] · 0.5DMF (2), with different structures have been synthesized by using substituted aroylhydrazones, 5-bromo-salicylaldehyde-benzoylhydrazone (H2L1) and 5-bromo-salicylaldehyde-3,5-dimethoxy-benzoylhydrazone (H2L2), and mono/bidentate heterocycles, imidazole (Himdz) and 1,10-phenanthroline (phen). Their crystal structures and spectroscopic properties have been studied. X-ray analysis show a distorted square-planar geometry for 1 and a distorted square-pyramidal geometry for 2, in which the chelating phen ligand displays axial-equatorial bonding. In both structures the ONO tridentate ligand occupies the basal plane. Self-assembly via O–H ··· N, N–H ··· O and C–H ··· O interactions lead to one-dimensional chain arrangement in 1 and 2. 相似文献
19.
《Journal of Coordination Chemistry》2012,65(16):2798-2809
A series of tetranuclear lanthanide compounds, [Ln4(μ3-OH)2L4(NO3)2(DMF)2] (H2L = 2-(2-hydroxy-3-methoxybenzylideneamino)phenol; Ln = Dy (1); Tb (2); Er (3); and Gd (4)), have been prepared under hydrothermal conditions. X-ray crystal structure analysis reveals that 1–4 are polymorphs. The cores of the structures can be described as co-planar defect-dicubane. The solid-state luminescent properties indicate that the LnIII ions have very deep influence on the luminescence of H2L. The magnetic properties for 1–4 were studied. The Dy4 complex exhibits single-molecule magnet behavior. 相似文献
20.
《Journal of Coordination Chemistry》2012,65(24):4237-4254
Seven new transition metal complexes formulated as [M2(1,4-tpbd)(diimine)2(H2O)2]4+ [M = Zn, Co, Ni, Cd; 1,4-tpbd = N,N,N′,N′-tetrakis(2-pyridylmethyl)benzene-1,4-diamine; diimine is a N,N-donor heterocyclic base like 1,10-phenanthroline (phen), 2,2′-bipyridine (bpy), 4,5-diazafluoren-9-one (dafo)] have been synthesized and structurally characterized by X-ray crystallography: [Zn2(1,4-tpbd)(phen)2(H2O)2]4+ (1), [Zn2(1,4-tpbd)(bpy)2(H2O)2]4+ (2), [Co2(1,4-tpbd)(phen)2(H2O)2]4+ (3), [Ni2(1,4-tpbd)(phen)2(H2O)2]4+ (4), [Ni2(1,4-tpbd)(bpy)2(H2O)2]4+ (5), [Ni2(1,4-tpbd)(dafo)2(H2O)2]4+ (6) and [Cd2(1,4-tpbd)(phen)2(H2O)2]4+ (7). Single crystal diffraction reveals that the metals in the complexes are all in a distorted octahedral geometry. The interactions of the seven complexes with calf thymus DNA (CT-DNA) have been investigated by UV absorption, fluorescence, circular dichroism spectroscopy and viscosity measurements. The apparent binding constants (Kapp) are calculated to be 5.2?×?105 M?1 for 1, 1.05?×?105 M?1 for 2, 5.76?×?105 M?1 for 3, 4.57?×?105 M?1 for 4, 1.29?×?105 M?1 for 5, 1.7?×?105 M?1 for 6, 2.53?×?105 M?1 for 7, the binding propensity to the calf thymus DNA in the order: 3 (Co-phen) > 1 (Zn-phen) > 4 (Ni-phen) > 7 (Cd-phen) > 6 (Ni-dafo) > 5 (Ni-bpy) > 2 (Zn-bpy). Furthermore, these complexes display efficient oxidative cleavage of supercoiled DNA; the Zn(II)/H2O2 and Cd(II)/H2O2 systems efficiently cleave DNA attributed to the peroxide ion coordinated to the Zn(II) and Cd(II), which enhanced their nucleophilicity, this is rare. 相似文献