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1.
《Inorganica chimica acta》1988,142(1):95-100
Four tetradentate nitrogen donor ligands have been prepared by condensation of N-hydroxymethylpyrazoles with ethylenediamines. These ligands are varied by methylation of the pyrazole rings (edbd) or the aminonitrogens (debp), or both (debd). Copper(II) complexes of the type CuL(ClO4)2 have been isolated with L = debp, edbp, edbd. For L = debd, the adducts salts Cu(debd)(dMp)X2, with X = ClO4−, BF4− and dMp = 3,5-dimethylpyrazole, were obtained. The compounds were characterized by their absorption (d-d) and EPR spectra. All four undergo quasi-reversible electrochemical reduction in methanol, the redox potentials being correlated with the degree of ligand methylation. The copper(I) forms are relatively unstable, and also bind carbon monoxide with different affinities. 相似文献
2.
R.N Patel Nripendra Singh U.K Chauhan J Niclós-Gutiérrez 《Inorganica chimica acta》2004,357(9):2469-2476
Two new mixed ligand complexes of copper(II) with N,N,N′,N″,N″-pentamethyldiethylenetriamine and polypyridine ligands have been prepared and characterized by means of spectroscopic, magnetic and single-crystal X-ray diffraction methods. These two complexes are isomorph and isostructure in which the coordination polyhedron about the copper(II) ion is distorted square pyramidal. [Cu(PMDT)(bipy)]2+ and [Cu(PMDT)(phen)]2+ show an absorption wavelength maximum at 625 and 678 nm, respectively, assigned to the d-d transition. Antibacterial, antifungal and superoxide dismutase activities of these complexes have also been measured. It was observed that [Cu(PMDT)(bipy)](ClO4)2 was more effective against P. Pyocyanea and Klebsiella sp. than S. aureus. Similarly, Fusarium sp. was highly susceptible against [Cu(PMDT)(bipy)](ClO4)2 but less susceptible against [Cu(PMDT)(phen)](ClO4)2. 相似文献
3.
Catalin Maxim Traian D. Pasatoiu Victor Ch. Kravtsov Sergiu Shova Christopher A. Muryn Richard E.P. Winpenny Floriana Tuna Marius Andruh 《Inorganica chimica acta》2008,361(14-15):3903-3911
The following Schiff bases were employed as ligands in synthesizing copper(II) and zinc(II) complexes: N-[(2-pyridyl)-methyl]-salicylimine (Hsalampy), N-[2-(N,N-dimethyl-amino)-ethyl]-salicylimine (Hsaldmen), and N-[(2-pyridyl)-methyl]-3-methoxy-salicylimine (Hvalampy). The first two ligands were obtained by reacting salicylaldehyde with 2-aminomethyl-pyridyne and N,N-dimethylethylene diamine, respectively, while the third one results from the condensation of 3-methoxysalicylaldehyde with 2-aminomethyl-pyridine. Four new coordination compounds were synthesized and structurally characterized: [Cu(salampy)(H2O)(ClO4)] 1, [Cu2(salampy)2(H2trim)2] 2 (H2trim? = the monoanion of the trimescic acid), [Cu4(valampy)4](ClO4)4 · 2CH3CN 3, and [Zn3(saldmen)3(OH)](ClO4)2 · 0.25H2O 4. The crystal structure of 1 consists of supramolecular dimers resulted from hydrogen bond interactions established between mononuclear [Cu(salampy)(H2O)(ClO4)] complexes. Compound 2 is a binuclear complex with the copper ions connected by two monoatomic carboxylato bridges arising from two molecules of monodeprotonated trimesic acid. The crystal structure of 3 consists of tetranuclear cations with a heterocubane {Cu4O4} core, and perchlorate ions. Compound 4 is a trinuclear complex with a defective heterocubane structure. The magnetic properties of complexes 1–3 have been investigated. Compound 4 exhibits solid-state photoluminescence at room temperature. 相似文献
4.
《Inorganica chimica acta》1986,114(1):9-14
A series of metal perclorate complexes of N- isopropyl-2-pyrrolidinone (NIPP) and N-cyclohexyl- 2-pyrrolidinone (NCHP) have been synthesized, showing coordination through the carbonyl oxygen atom. These complexes have compositions with the general formulas [M(NIPP)4 or 6]2+(ClO4)2 and [M(NCHP)6]2+(ClO4)2 [M = Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II)]. They have been characterized by IR spectra, electrical conductivity measurements, magnetic moments, X-ray diffraction patterns and electronic absorption spectra. 相似文献
5.
Reaction of the ligand N-methyl-N-((6-pivaloylamido-2-pyridyl)methyl)-N-(2-pyridylethyl)amine (mpppa) with equimolar amounts of [Cu(H2O)6][ClO4]2 or CuCl2 · 2H2O in MeCN afforded mononuclear copper(II) complexes [Cu(mpppa)][ClO4]2 (1) and [Cu(mpppa)Cl2] (2). Crystal structure analysis reveals CuN3O (two pyridyl, an aliphatic amine, and an amide oxygen) coordination in 1 and CuN3Cl2 (two pyridyl, an aliphatic amine, and two chlorides) coordination in 2. Crystal packing diagram of 1 reveals that one of the perchlorate counteranions provides weak coordination to copper(II) centers and in turn the copper(II) centers assume pseudo-six-coordination, generating 1D chain. Notably, one of the copper(II)-coordinated chloride ions in 2 participates in an intramolecular N–H?Cl interaction. Intermolecular C–H?Cl interactions in the solid state generate helical structure. Spectroscopic (IR, UV–Vis, and EPR) and redox properties of the two complexes have been investigated and compared. 相似文献
6.
Copper(II) complexes of new N3O- and N2O2-donor tripodal ligands bearing one or two o-substituted phenol moieties have been synthesized as models for the galactose oxidase active site. The complexes of 2-[N-(1-methyl-2′-imidazolylmethyl)-N-(6″-methyl-2″-pyridylmethyl)-aminomethyl)]-4-methyl-6-methylthiophenol (MeSL), [Cu(MeSL)Cl], and N-(6-methyl-2-pyridylmethyl)-N,N-bis(2′-hydroxy-3′,5′-di-tert-butylbenzyl)amine (t-buL2mepy), [Cu(t-buL2mepy)(H2O)], have been revealed by X-ray structural analysis to have a square-pyramidal structure with one and two phenolate oxygens in the basal plane, respectively. [Cu(MeSL)Cl] was converted into a Cu(II)-o-methylthiophenoxyl radical species by electrochemical or Ce(IV) oxidation. An o-methoxyphenoxyl radical in a similar complex was considerably more stable than the 2,4-di(tert-butyl)phenoxyl radical. While t-buL2mepy reacted with Cu(ClO4)2 to give [Cu(t-buL2mepy)(H2O)] without disproportionation, an N2O2-donor ligand containing an o-methoxyphenol, a 2,4-di(tert-butyl)phenol, and an N-methylimidazole moiety gave a phenoxyl radical complex exhibiting the characteristic absorption peak at 478 nm as a reddish powder by the reaction with Cu(ClO4)2 as a result of spontaneous disproportionation. It exhibited a quasi-reversible redox wave at E1/2=0.34 V (vs. Ag/AgCl) in CH3CN, which is lower than the potentials of the copper complexes of various N3O-donor ligands, and oxidized ethanol to acetaldehyde with a low turnover number. 相似文献
7.
Xue-Feng Huang 《Inorganica chimica acta》2005,358(6):2097-2100
The reaction of N,N-(2-pyridyl)(4-pyridylmethyl)amine with [Cu(MeCN)2(PPh3)2]ClO4 in the presence of THF affords a novel one-dimensional copper(I) coordination polymer {[Cu(PPh3)(N,N-(2-pyridyl)(4-pyridylmethyl)amine)](ClO4)}n (1), which crystallizes in an noncentrosymmetric space group and displays strong second-harmonic generation (SHG) response. 相似文献
8.
Two trinuclear copper(II) complexes of a Schiff-base type N4O-donor ligand (LH) derived from 4,4,9,9-tetramethyl-5,8-diazadodecane-2,11-dione and 1,3-diaminopropan-2-ol are reported. Complex [Cu3L2(ClO4)4] (1) has an angular C2-symmetric trinuclear core as revealed from single-crystal X-ray diffraction studies. The terminal coppers are in square-pyramidal geometry with an N3O2 coordination environment while the central one is in octahedral geometry with an N2O4 donor environment. Complex [Cu3L2(ClO4)(N3)(H2O)](ClO4)2 · H2O (2) has an unsymmetrical trinuclear core with an intramolecular hydrogen bonding interaction between the water and azide anion coordinated to Cu(1) and Cu(3) center, respectively. All the copper centers in 2 are in square-pyramidal geometry. The average Cu?Cu distance between closest metal ions in both the complexes is 3.897 Å. The coordination environment of coppers in 1 approximately mimics that of multicopper oxidases in the oxidized form and the environment in 2 mimics that of the azide derivative of ascorbate oxidase. Both 1 and 2 exhibit doublet spin ground state due to strong antiferromagnetic coupling operating through the alkoxo-bridged oxygen atoms between the copper centers. 相似文献
9.
A 14-membered tetraaza macrocycle, 2,13-bis(2-carbomethoxyethyl)-5,16-dimethyl-2,6,13,17-tetraazatricyclo[16.4.0.1.1807.12]docosane (L2) bearing two N-CH2CH2COOMe groups, and its nickel(II) and copper(II) complexes have been prepared and characterized. The nickel(II) and copper(II) complexes of 2-(2-carbomethoxyethyl)-5,16-dimethyl-2,6,13,17-tetraazatricyclo[16.4.0.1.1807.12]docosane (L3) containing one N-CH2CH2COOMe group have also been prepared. The crystal structure of [NiL2](ClO4)2 shows that the complex has a slightly distorted trans-octahedral coordination geometry with two relatively short axial Ni-O (N-CH2CH2COOMe group) bonds (2.136(3) Å). In various solvents, however, a considerable proportion of [NiL2]2+ exists as a square-planar form, in which the functional pendant arms are not involved in coordination. The proportion of the square-planar isomer varies with solvents in the order of nitromethane ? acetonitrile < H2O < DMF ? DMSO. In the case of [CuL2](ClO4)2, only one N-CH2CH2COOMe group is involved in coordination. The N-CH2CH2COOMe group of [NiL3](ClO4)2 is not directly involved in coordination even in the solid state, though the functional group of [CuL3](ClO4)2 is coordinated to the metal ion. 相似文献
10.
A series of new copper(II) complexes of four sterically hindering linear tridentate 3N ligands N′-ethyl-N′-(pyrid-2-ylmethyl)-N,N-dimethylethylenediamine (L1), N′-benzyl-N′-(pyrid-2-ylmethyl)-N,N-dimethylethylenediamine (L2), N′-benzyl-N′-(6-methylpyrid-2-yl-methyl)-N,N-dimethylethylenediamine (L3) and N′-benzyl-N′-(quinol-2-ylmethyl)-N,N-dimethylethylenediamine (L4) have been isolated and examined as catalysts for olefin aziridination. The complexes [Cu(L1)Cl2]·CH3OH 1, [Cu(L2)Cl2]·CH3OH 2, [Cu(L3)Cl2]·0.5 H2O 3 and [Cu(L4)Cl2] 4 have been structurally characterized by X-ray crystallography. In all of them copper(II) adopts a slightly distorted square pyramidal geometry as inferred from the values of trigonality index (τ) for them (τ: 1, 0.02; 2, 0.01; 3, 0.07; 4, 0.01). Electronic and EPR spectral studies reveal that the complexes retain square-based geometry in solution also. The complexes undergo quasireversible Cu(II)/Cu(I) redox behavior (E1/2, −0.272 − −0.454 V) in acetonitrile solution. The ability of the complexes to mediate nitrene transfer from PhINTs and chloramine-T trihydrate to olefins to form N-tosylaziridines has been studied. The complexes 3 and 4 catalyze the aziridination of styrene very slowly yielding above 80% of the desired product. They also catalyze the aziridination of the less reactive olefins like cyclooctene and n-hexene but with lower yields (30-50%). In contrast to these two complexes, 1 and 2 fail to catalyze the aziridination of olefins in the presence of both the nitrene sources. All these observations have been rationalized based on the Cu(II)/Cu(I) redox potentials of the catalysts. 相似文献
11.
A new macropolycycle, 2,13-dimethyl-1,5,12,16-tetraazapentacyclo[14.6.2.25.12.06.11.017.22]hexacosane (L3), has been prepared by the reaction of 3,14-dimethyl-2,6,13,17-tetraazatricyclo[16.4.0.07.12]docosane (L1) with 1-bromo-2-chloroethane. The macropolycycle readily reacts with anhydrous copper(II) ion to yield [CuL3]2+ in dry methanol but does not with nickel(II) ion, showing a high copper(II) ion selectivity. Crystal structure of [CuL3](ClO4)2 shows that the complex has a distorted square-planar coordination polyhedron with a trans-IV type N-conformation. The Cu-N distances [1.989(3) and 2.015(3) Å] of [CuL3](ClO4)2 are distinctly shorter than those of [CuL1](ClO4)2 and other related macrocyclic copper(II) complexes. The d-d transition band for [CuL3](ClO4)2 is observed at 447 nm, which is ca. 40 nm shorter than that for [CuL1](ClO4)2. 相似文献
12.
Kowalik-Jankowska T Biega L Kuczer M Konopińska D 《Journal of inorganic biochemistry》2008,102(8):1615-1622
The stoichiometry, stability constants and solution structure of the complexes formed in the reaction of copper(II) with hexapeptide NPTNLH, i.e. the Neobelliera Bullata Trypsin Modulating Oostatic Factor (Neb-TMOF), and its analogues DPTNLH, Ac-NPTNLH and Ac-DPTNLH have been determined by potentiometric, UV-visible, CD and EPR spectroscopic methods. Upon raising pH for Ac-NPTNLH and Ac-DPTNLH peptides, copper(II) coordination starts from the imidazole nitrogen of the His6; afterwards three deprotonated amide nitrogens are progressively involved in metal ions coordination. In a wide pH range of 4.5-8.5 for the NPTNLH and DPTNLH ligands the CuL complex dominates with the imidazole nitrogen of His6 coordinated to form a macrochelate. The N-terminal amino group of the NPTNLH and DPTNLH peptides takes part in the coordination of the metal ion in the CuL, CuH−1L and CuH−2L complexes. However, at pH above 9 the CuH−3L complex with the {NIm, 3N−} coordination mode is formed. For the CuH−2L complex the spectroscopic data clearly indicate the 4N {NH2, CO or COO−, 2N−, NIm} bonding mode with the axial coordination of the N-terminal amine group to the metal ion. 相似文献
13.
《Inorganica chimica acta》1986,115(2):141-146
A series of new aromatic N-oxide ligands have been prepared by converting the 2-amino group of 2-aminopyridine N-oxide, 2-aminopicoline N-oxides and 2-amino-4,6-lutidine N-oxide into a urethane. Two series of copper(II) complexes have been prepared and characterized by their infrared, electronic and ESR spectra along with other physicochemical methods. One series has the stoichiometry [Cu(UOH)4](ClO4)2 and involves monodentate coordination via the N-oxide oxygen and the other series is prepared from copper(II) acetate and has the stoichiometry [Cu(UO)2]. In this latter series coordination occurs via the N-oxide oxygen and the deprotonated amino function. 相似文献
14.
P.M. Vimal Kumar 《Inorganica chimica acta》2011,375(1):84-92
The Schiff base ligand, 4-isopropylbenzaldehyde[N-(3-oxo-3,4-dihydro-2-quinoxalinyl)hydrazone] (Ipbh), the 1:1 condensation product of 4-isopropylbenzaldehyde and 2-hydroxy-3-hydrazinoquinoxiline, has been synthesized and characterized by X-ray crystallography. A series of complexes of Ipbh with Nickel(II), viz., [Ni(Ipbh)2]Cl2 (1), [Ni(Ipbh)2]Br2 (2), [Ni(Ipbh)2]I2 (3), [Ni(Ipbh)2·(CH3OH)2](NO3)2·(CH3OH)2 (4) and [Ni(Ipbh)2ClO4]ClO4 (5) have been synthesized. All the complexes were characterized by elemental analysis, molar conductivity, CHN analysis, spectroscopic studies, magnetic susceptibility measurements and TG/DTA methods. The solid-state structure of the complex 4 was established by single crystal X-ray crystallography. In all the complexes, Ipbh acts as a bidentate NO chelating agent, coordinated to the metal ion through the imine nitrogen and quinoxaline oxygen. In complex 4, Nickel(II) is in a distorted octahedral environment with an identical set of donor atoms, N2O4, coming from two imine nitrogen and two quinoxaline oxygen atoms of two Ipbh moieties as well as two oxygen atoms of the two methanol molecules. The crystal packing of Ipbh and the complex 4 exhibits 1D and 2D supramolecular networks, respectively through different intermolecular hydrogen-bonding interactions. 相似文献
15.
Mitchell R. Malachowski Mark E. Adams Ryan White Arnold L. Rheingold Richard S. Kelly 《Inorganica chimica acta》2009,362(4):1247-1252
Two nitrogen and sulfur containing ligands, 1-methyl-4-((4-methylimidazol-5-yl)methylthio)benzene (NS-mim) (1) and 1-methyl-4-(2-pyridylmethylthio)benzene (NS-mpy) (2) were synthesized and a series of their Cu(II) complexes, 3-10, prepared. The imidazole-containing complexes (3-6) have the form [Cu(NS-mim)2(solvent)2](X)2 where X = ClO4, BF4and [Cu(NS-mim)2(Y)2] where Y = Cl or Br and the pyridine-containing complexes (7-10) have the form [Cu(NS-mpy)2]X2 (where X = ClO4, BF4) and [Cu2(NS-mpy)2Y4] (where Y = Cl or Br). These complexes were characterized by a combination of elemental analysis, FAB-MS and electrochemistry. The X-ray structure of the imidazole-containing [Cu(NS-mim)2(DMF)2](ClO4)2 (3) was determined and it showed the copper(II) coordinated only by the nitrogen donors while the sulfurs remain uncoordinated. In comparison, the X-ray structure of the pyridine-containing [Cu2(NS-mpy)2(Cl)4] (9) shows a dinuclear copper(II) complex with the nitrogens and the sulfurs coordinated along with a terminal chloride and two μ-chloro atoms bridging the coppers. Cyclic voltammetry studies indicated that the complexes undergo quasi-reversible one-electron reductions in acetonitrile at potentials between 0.31 and 0.51 V versus SCE. The complexes were found to be active for the oxidation of di-tert-butyl catechol (DTBC) with the rate dependent on the ligand and the counterion present. 相似文献
16.
Jörg Astner Simon P. Foxon Frank W. Heinemann Rajeev Gupta Rabindranath Mukherjee 《Inorganica chimica acta》2008,361(1):279-292
The reaction of dioxygen with the copper(I) complex of the tridentate ligand 1,1,4,7,7-pentamethyldiethylenetriamine (Me5dien) has been investigated using low-temperature stopped-flow techniques. The formation of a bis(μ-oxo)copper(III) complex as a reactive intermediate could be detected spectroscopically at low temperatures and a quantitative kinetic analysis was performed for this system. Crystal structures of the copper(II) complexes [(Me-bpa)Cu(Cl)2] (1), [{(Me-bpa)Cu(Cl)(ClO4)}2] (2), [{(MeL)Cu(Cl)(ClO4)}2] (3), and [(MeL)Cu(NCS)2] (4) (Me-bpa = N-methyl-[bis(2-pyridyl)methyl]amine; MeL = N-methyl-[(2-pyridyl)ethyl(2-pyridyl)methyl]amine) are reported. 相似文献
17.
Maura Pellei Mercedes Camalli Giancarlo Gioia Lobbia Grazia Papini Carlo Santini 《Inorganica chimica acta》2008,361(5):1456-1462
Copper(I) complexes have been synthesized from the reaction of CuCl, monodentate tertiary phosphines PR3 (PR3 = P(C6H5)3; P(C6H5)2(4-C6H4COOH); P(C6H5)2(2-C6H4COOH); PTA, 1,3,5-triaza-7-phosphaadamantane; P(CH2OH)3, tris(hydroxymethyl)phosphine) and lithium bis(3,5-dimethylpyrazolyl)dithioacetate, Li[LCS2]. Mono-nuclear complexes of the type [LCS2]Cu[PR3] have been obtained and characterized by elemental analyses, FT-IR, ESI-MS and multinuclear (1H, 13C and 31P) NMR spectral data; in these complexes the ligand behaves as a κ3-N,N,S scorpionate system. One exception to this stoichiometry was observed in the complex [LCS2]Cu[P(CH2OH)3]2, where two phosphine co-ligands are coordinated to the copper(I) centre. The solid-state X-ray crystal structure of [LCS2]Cu[P(C6H5)3] has been determined. The [LCS2]Cu[P(C6H5)3] complex has a pseudo tetrahedral copper site where the bis(3,5-dimethylpyrazolyl)dithioacetate ligand acts as a κ3-N,N,S donor. 相似文献
18.
Mark B. Bushuev Eugenia V. Peresypkina Alexander V. Virovets Oleg P. Shkurko 《Inorganica chimica acta》2011,365(1):384-390
A series of copper(II) complexes, i.e. Cu2LCl4, CuLCl2·H2O and [Cu2L2Cl4]·2MeCN (8), based on a new potentially polytopic ligand, 3,5-bis(4,6-dimethylpyrimidin-2-yl)-4H-1,2,4-triazol-4-amine (3b, L), have been synthesized. The crystal structures of L and [Cu2L2Cl4]·2MeCN were studied by X-ray single crystal analysis. The dinuclear compound [Cu2L2Cl4]·2MeCN represents the first example of structurally characterized metal complexes with 3,5-di(pyrimidin-2-yl)-4H-1,2,4-triazol-4-amines. Both copper atoms have distorted tetragonal-pyramidal 3N + 2Cl environment. Surprisingly, in contrast to the complexes based on 3,5-di(pyridin-2-yl)-4H-1,2,4-triazol-4-amine (pyridinyl analog of L), the compound [Cu2L2Cl4]·2MeCN adopts a dinuclear trans-(N′,N1,N2)2 double bridging binding mode which is due to tridentate coordination of two L molecules linking two copper atoms through N1,N2-triazole and N′-pyrimidine atoms. It seems to be reasonable that it is methyl groups in pyrimidinyl moiety that obstruct the expected dinuclear (N′,N1,N2,N″)2 double bridging coordination being one of the most common for 4-substituted 3,5-di(pyridin-2-yl)-4H-1,2,4-triazoles and 3,5-di(pyridin-2-yl)-1,2,4-triazolates. Due to π-π stacking interactions, molecules of Cu2L2Cl4 in the structure of [Cu2L2Cl4]·2MeCN form 1D chains. 相似文献
19.
A series of mononuclear iron(III) complexes with containing phenolate donor of substituted-salicylaldimine based ligands [Fe(L1)(TCC)] · CH3OH (1), [Fe(L2)(TCC)] · CH3OH (2), [Fe(L3)(TCC)] (3), and [Fe(L4)(TCC)] (4) have been prepared and studied as functional models for catechol dioxygenases (H2TCC = tetrachlorocatechol, or HL1 = N′-(salicylaldimine)-N,N-diethyldiethylenetriamine, HL2 = N′-(5-Br-salicylaldimine)-N,N-diethyldiethylenetriamine, HL3 = N′-(4,6-dimethoxy-salycyl-aldimine)-N,N-diethyl-diethylenetriamine, HL4 = N′-(4-methoxy-salicylaldimine)-N,N-diethyl-diethylenetriamine). They are structural models for inhibitors of enzyme-substrate adducts from the reactions of catechol 1,2-dioxygenases. Complexes 1-4 were characterized by spectroscopic methods and X-ray crystal structural analysis. The coordination sphere of Fe(III) atom of 1-4 is distorted octahedral with N3O3 donor set from the ligand and the substrate TCC occupying cis position, and Fe(III) is in high-spin (S = 5/2) electronic ground state. The in situ prepared iron(III) complexes without TCC, [Fe(L1)Cl2], [Fe(L2)Cl2], [Fe(L3)Cl2], and [Fe(L4)Cl2] are reactive towards intradiol cleavage of the 3,5-di-tert-butylcatechol (H2DBC) in the presence of O2 or air. The reaction rate of catechol 1,2-dioxygenase depends on the redox potential and acidity of iron(III) ions in complexes as well as the substituent effect of the ligands. We have identified the reaction products and proposed the mechanism of the reactions of these iron(III) complexes with H2DBC with O2. 相似文献
20.
Four copper(II) complexes [Cu2(1,3-tpbd)Cl4]·EtOH (1), {[Cu2(1,3-tpbd)(μ-Cl)2](ClO4)2(H2O)4.5 (NaClO4)}∞ (2), [Cu2(1,3-tpbd)(1,10-phen)2(H2O)2](ClO4)4 (3) and [Cu2(1,3-tpbd)(2,2′-bpy)2(H2O)2](ClO4)4 (4) (1,3-tpbd = N,N,N′,N′-tetrakis(2-pyridylmethyl)benzene-1,3-diamine) have been synthesized and characterized by X-ray single crystal structure analysis. Variable-temperature magnetic susceptibility studies (2-300 K) indicate the existence of antiferromagnetic coupling between the copper(II) ions in complexes 2 and 3. The interactions of the four complexes with calf thymus DNA (CT-DNA) have been investigated by UV absorption, fluorescent spectroscopy, circular dichroism spectroscopy, viscosity and cyclic voltammetry, and the modes of CT-DNA binding to the complexes have been proposed. Furthermore, DNA cleavage activities by the four complexes were performed in the presence and absence of external agents, the results indicate that their cleavage activities have been promoted in the presence of external agents. Mechanism investigation shows that the four complexes could cleave DNA through both oxidative and hydrolytic processes. In the four copper(II) complexes, complex 2 showed highest cleavage activity with the pseudo-Michaelis-Menten kinetic paraments kcat = 5.16 h−1 and Km = 3.6 × 10−5 M. 相似文献