Synthesis and properties of the copper(Ⅱ) complexes with stable radical

Four novel copper(Ⅱ) complexes have been synthesized,namely Cu(hfac)2NITPhNO2 (1),Cu(hfac)2NITPhCH3 (2),Cu(pfpr)2NITPhNO2,(3) and Cu(Pfpr)2NITPhCH3 (4),where hfac= hexafluoro-acetylacetonate,pfpr=pentafluoropropionate,NITR.=2-R-4,4,5,5-tetraniethyl-4,5-dihydro-1H-imidazolyl-1-oxyl-3-oxide.(R=4-nitrophenyl,4-methylphenyl).These complexes were rharicter-ized by elemental analyses,IR,electronic spectra and molar conductance.The temperature-dependent magnetic susceptibility of complexes 1 and 3 have been studied in the 4 300 K range,giving I he exchange integral J=10.56 cm-1 for complex 1 and J =-30.9 cm-1 for complex 3.     

Synthesis and Crystal Structures of the α and β Forms of Bis(salicylaldoxime)copper(Ⅱ) Complexes

Modified α and β bis(salicylaldoxime)copper(Ⅱ) have been obtained by recrystallization from ethyl acetate(CCDC Nos. 212157 & 212158). The X-ray analysis reveals that the two modificated forms have the same structure with different geometric parameters. The α form crystallizes in the P2(1)/c space group and the β form in the P1 space group. Both the crystal structures consist of centrosymmetric monomeric molecules of Cu(OC6H4CNOH)2. The IR spectra are in agreement with the structural data.     

Synthesis and Crystal Structure of Tetrakis(1-vinylimidazole-kN3)diisothiocyanatomanganese(Ⅱ)

The title compound I(C22H24MnN10S2,Mr=547.57)has been synthesized and structurally characterized by single-crystal X-ray diffraction.The compound crystallizes in the monoclinic system,space group P21/c with a=8.6010(17),b=9.0180(18),c=17.773(4)(A),β=101.79(3)°,V=1349.5(5)(A)3,Z=2,Dc=1.348 g/cm3,μ=0.674mm-1,F(000)=566,the final R=0.0488 and wR=0.1289.In the structure,each Mn atom is coordinated by four Vim(Vim=1-vinylimidazole)ligands and a pair of monodentate isothiocyanic groups,affording a compressed octahedral MnN6 core.     

Synthesis and Properties of u-Oxamido Heterobinuclear Cu(Ⅱ)-Co(Ⅱ) Complexes

Three heterobinuclear complexes were synthesized, namely [Cu (oxpn) Co (L)2] (ClO4)2·xH2O(L= 2,2'-bipyridyl(bpy), 1,10-phenanthroline(phen) , and 5-nitro-1, 10-phenanthroline (NO2-phen)), where oxpn represents N, N'-bis(3-aminopropyl) oxam-ido. Based on 1R, elemental analysis, conductivity measurement and electronic spectra, these complexes were characterized by an extended oxamido-bridged structure with Cu(Ⅱ) in a planar environment and Co(Ⅱ) in a octahedral environment. The symmetry of the cation is very close to C2v.The complexes were also characterized with variable temperature (4~300K) magnetic susceptibility, and the data were fit for the susceptibility equation derived from spin Hamilton, H= -2JS1.S2-DSx12 by least square strategy. The exchange integral, J, was found to be -22.36 cm-1 (for bpy);-15.45 cm-1 (for phen); -19. 10cm-1(for NO2-phen), indicating that there is a weak antiferromagnetic spin-exchange interaction between the metal ions.     

Studies of copper (Ⅱ) complexes as catalysts for the hydrolysis of DNA

Hydrolysis of DNA is an important enzymatic reaction , but it is exceedingly difficult to mimic in the laboratory because of the stability of hydrolysis of DNA. In this paper, the cleavage activity of complexes formed between Cu(Ⅱ) and four different amino acid or amino acid methyl ester on DNA is studied by gel elec-trophoresis. It is found that DNA could be cleaved by Cu(Ⅱ)-L-His and Cu(Ⅱ)-L-His methyl ester complexes and the efficiency of cleavage is largely dependent on the metal ion-to-ligand ratio. Further experiments show that the cleavage of DNA mediated by Cu(Ⅱ)-L-His complexes occurs via a hydrolytic mechanism and the active chemical species that affects DNA cleavage is proposed to be MI2H and ML2H22 .     

Syntheses and Crystal Structures of Two New Zinc(Ⅱ)Nitroxide Radical Complexes Bridged by Isophthalate

Two novel complexes [Zn(NIT3-py)(ip)]n 1 and [Zn(im3-py)(ip)]n 2 (NIT3-py =2-(3"-pyridyl)-4,4,5,5,-tetramethylimidazoline-1-oxyl-3-oxide, im3-py = 2-(3'-pyridyl)-4,4,5,5-te-tramethylimidazoline-1-oxyl, ip = isophthalate) have been synthesized and structurally determinedby X-ray diffraction.Crystal data for 1: C32H36N6O8Zn, Mr= 698.04, monoclinic, space group C with a = 23.600(3), b = 10.2073(12), c = 13.4027(16)(A), β= 92.586(2)°, V = 3225.3(7) (A)3, Dc=1.438 g/cm3, F(000) = 1456,μ(MoKα) = 0.822 mm-1, Z = 4, the final R = 0.0390 and wR = 0.1032 for 6037 independent reflections with Rint=0.0214.Crystal data for 2: C32H36N6O6Zn, Mr = 666.04,monoclinic, space group C2/c with a = 24.434(4), b = 13.543(2), c = 10.2379(16)(A), β= 109.024(2)°,V= 3202.8(9)(A)3, Dc= 1.381 g/cm3, F(000) = 1392,μ(MoKα) = 0.820 mm-1, Z= 4,the final R = 0.0304 and wR = 0.0658 for 2833 independent reflections with Rint = 0.0307.X-ray analysis reveals that both Zn(Ⅱ) ions are four-coordinated by two pyridyl-N atoms from nitroxide radicals and two carboxylate oxygen atoms to form distorted tetrahedral geometries.Each iso-phthalate dianion binds two Zn(Ⅱ) ions in a monodentate mode, leading to a 1-D chain structure.     

Synthesis and magnetic interaction of μ-2-chloroterephthalato binuclear iron (Ⅱ) complexes

Four μ-2-chloroterephthalato binuclear iron(Ⅱ) complexes, namely [Fe2 (CTPHA) L4]-(ClO4)2, where L stands for 4,4'-dimethyl-2,2'-bipyridine (Me2-bpy); 2,9-dimethyl-l, 10-phenanthro-line (Me2-phen); 5-chloro-l, 10-phenanthroline (Cl-phen); 4, 7-diphenyl-l, 10-phenanthroline (Ph2-phen), respectively, and CTPHA represents 2-chlorolerephthalate dianion, have been synthesized and characterized. Based on the elemental analyses, molar conductance measurements and spectroscopic studies, extended CTPHA-bridged structures consisting of two iron(Ⅱ) ions, each in a distorted octahedral environment, are proposed for these complexes. [Fe2 CTPHA)-(Me2-bpy)4] (ClO2 (1) and [Fe2(CT-PHA)·(Me2-phen)4](ClO4)2 (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, H = - 2JS1 · S2 , giving the exchange integrals J = - 1.28 cm-1 for 1 and J = - 1.85 cm-1 for 2. These r     

Theoretical study on second-order nonlinear optical properties of 1,10-phenanthroline Ru(Ⅱ) complexes

The dynamic first hyperpolarizabilities of a series of 1,10-phenanthroline Ru(Ⅱ) complexes were carried out using density functional theory(DFT).The results indicate that these complexes have large second-order nonlinear optical(NLO) responses.Specially,complex 6b has a maximal first hyperpolarizability βtot value.The first hyperpolarizabilities can be tuned by changing the ancillary ligand,introducing electron-acceptor group NO2 and/or increasing π-conjugation on phenanthroline.Calculations on absorption spectra demonstrate that the second-order NLO responses of complexes in series a are ascribed to the intraligand charge transfer(ILCT),while the complexes in series b exhibit metal-to-ligand charge transfer(MLCT) and ligand-to-ligand charge transfer(LLCT) transition at relatively low-energy absorptions.     

Cyclometalated platinum(Ⅱ) complexes with sterically bulky camphor-derived groups as β-diketonate ancillary ligand:a new route to efficiently reducing π-π interactions and Pt-Pt interactions

A new series of mono-cyclometalated square planar platinum(Ⅱ) complexes have been synthesized and the single-crystal X-ray structures of complex 1 and 2 have been determined.The complexes have the general formula ppyPt(O^O),where ppy is 2-phenylpyridyl,and O^O is β-diketonate ancillary ligands with the acyl substituent group in position 3 of(D)-(+)-camphor.Although,like the many Pt(Ⅱ) complexes with square-planar geometry,these complexes have plane stacking modes in crystal structure,the sterically bulky ca...     

Synthesis,characterization and magnetism of copper(Ⅱ)-lan-thanide(Ⅲ) heterobimetalic complexes with N,N'-oxamidobis-(benzoato) cuprate (Ⅱ)

Seven new μ-oxamido copper(Ⅱ)-lanthanide(Ⅲ)hetero-bitnetalic complexes described by the fonnula Cu(obbz)Ln-(Ph-phen)2NO3(Ln=La,Nd,Eu,Gd,Tb,Ho,Er),where obbz denotes the oxamidobis(benzoato)and Ph-phen represents 5-phenyl-1,10-phenanthroline,have been synthesized and characterized by the elemental analyses,spectro-scopic(IR,UV,ESR)studies,magnetic moments(at room temperature)and molar conductivity measurement.The temperature dependence of the magnetic susceptibility of Cu(obbz)Gd(Ph-phen)2NO3 complex has been measured over the range 4.2-300 K.The least-squares fit of the experimental susceptibilities based on the spin Hamiltonian operator,H=-2JS1 S2,yielded J= 1.28 cm-1,a weak ferromagnetic coupling.A plausible mechanism for a ferromagnetic coupling between Gd(Ⅲ)-Cu(Ⅱ)is discussed in terms of spin-polarization.     

Synthesis,structures and magnetic properties of a series of polynuclear copper(Ⅱ)-lanthanide(Ⅲ) complexes assembled with carboxylate and hydroxide ligands

Heterometallic copper(Ⅱ)-lanthanide(Ⅲ) complexes have been made with a variety of exclusively O-donor ligands including betaines (zwitterionic carboxylates) and chloroac-etate,which are dinuclear CuLn,tetranuclear Cu2Ln2,pen-tanuclear Cu2Ln2,and octadecanuclear Cu12Ln6 complexes.Hie results show that subtle changes in both the carboxylates and acidity of the reaction solution can cause drastic changes in the structures of the products.Magnetic studies exhibit that shielding of the Ln3 4f electrons by the outer shell electrons is very effective to preclude significant coupling interaction between the Ln3 4f electrons and Cu2 3d electrons in either a mono-atomic hydroxide-bridged,or a carboxylate-bridged system.     

Synthesis and catalytic activity of novel heteronuclear Ln(Ⅲ)-Cu(Ⅱ) complexes with noncyclic polyether-amino acid Schiff base

A series of novel heteronuclear Ln(Ⅲ)-Cu(Ⅱ) complexes with noncyclic polyether-amino acid Schiff base were synthesized. The general formula is [LnCu_2(H_2TALY)(NO_3)_5](NO_3)_2' nH_2O(Ln=La, Nd, Sm, Gd, n= 4; Ln=Yb, Y, n=3), where H_2TALY = tetraglycol aldehyde bis-lysine Schiff base. It is the first time to report the synthetic method for this new Cu(Ⅱ) complexes and Ln(Ⅲ)-Cu(Ⅱ) heteronuclear complexes. The complexes were characterized by elemental analysis, IR spectra, TG-DTA, magnetic susceptibility, and especially by a 500 MHz NMR spectrometer for 2D-COSY NMR. Coordination mechanism and structures of complexes have been suggested as well. Of particular interest is the potential that the novel complexes obtained may be used as a catalyst, which prompted us to investigate them. It shows 100% conversion with the viscosity-average molecular weight 120 000 for the polymerization of methyl methacrylate (MMA) without addition of any cocatalyst. Furthermore, the complexes with such aliphatic Schiff bas     

Synthesis and Properties of Three Tris(1,10-phenanthroline) ruthenium (Ⅱ) Derivatives

MThekeymaterials,5-amino-l,10-phenanthrolineandetS-Ru(phew,CI,,werepreparedbythemethodsofreferences"'.Synthesisofla,foandicEquimolaramountsofcorrespondingto-bromo-alkyIacyIohIondewasaddeddropwisetoasuspensionof5-amino-l,10-phenanthrolineandsodiumdicarbonateindryacetonitrilewithstirringatroomtemperatureundernitrogenfor4-6hours.Thentheresultingsolidwasfilteredandwashedbyacetonitrile,5%sodiumbicarbonateaqueoussolutionandwaterinturn.Afterbeingdriedicvacuo,yellowmicrocrystalsla-cwereobtained.Sy…     

DFT and TDDFT investigations on the ground and excited states for polynuclear platinum(II) complexes containing the rigid phenylacetylide ligand

We have studied the ground and excited states of the three dendritic polynuclear Pt(II) complexes 1-[Cl(PH3)2PtC≡≡ C]-3,5-[HC≡≡ C]C6H3 (1), 1,3-[Cl(PH3)2PtC≡≡ C]2-5-[HC≡≡ C]C6H3 (2), and 1,3,5-[Cl(PH3)2- PtC≡≡ C]3C6H3 (3), by using the B3LYP and UB3LYP methods, respectively. TDDFT approach with the PCM model was performed to predict the emission spectra properties of 1―3 in CH2Cl2 solution. We first predicted the excited-state geometries for the three complexes. With the change of the number of Pt(II) atom, 1―3 show the different geometry structures in both the ground and excited states; fur- thermore, the increase of the metal density from 1 to 3 results in the red shift of the lowest-energy emissions along the series. The luminescent properties of 1 are somewhat different from those of 2 and 3. The emission properties of 2 and 3 are richer than 1. Our conclusion can give a good support for designing the high efficient luminescent materials.     

Dimerization of Propylene by Nickel (Ⅱ) and Cobalt (Ⅱ) Catalysts Based on Bidentate Nitrogen-phosphino Chelating Ligands

The catalytic property of propylene dimerization by several nickel (Ⅱ), cobalt (Ⅱ) complexes containing N-P bidentate ligands was studied in combination with organoaluminum co-catalysts. The effects of the type of aluminum co-catalysts and its relative amount, the nature of precursors in terms of ligand backbone and metal center were investigated. The results indicated that precursor I (N,N-dimethyl-2-(diphenylphosphino)aniline nickel (Ⅱ) dichloride) exhibited high activity in propylene dimerization in the presence of the strong Lewis acid Et3Al2Cl3, whereas low productivity by its cobalt analogues was observed under identical reaction conditions.     

Kinetics and Thermodynamics of the Adsorption of Copper(Ⅱ) onto a New Fe-Si Adsorbent

A new kind of Fe-Si adsorbent was synthesized by iron oxide and diatomite after calcining and hydrothermal process. The influences of the initial Cu2+ concentration, p H and adsorption time on the Cu2+ removal efficiency were discussed. Three adsorption empirical kinetics equations and two thermodynamics equations were used to simulate the adsorption process. The microstructures of newly developed copper removal materials and properties of copper removal are characterized in details by SEM and EDS. Adsorption mechanism of the adsorbent was discussed. The suitable p H value for Cu2+ removal is 5.0 to 6.0 and the adsorption capacity increases with increasing the initial Cu2+ concentration. The adsorption kinetics of the adsorbent could be better described by pseudo second order kinetic model, whereas the adsorption isotherms highly conform to the Freundlich equation. The main crystalline phase of the adsorbent is Fe(Si O3) which can build porous structures conducive to the Cu2+ adsorption.     

Bio-rational design of photosystem Ⅱ inhibitors (Ⅷ)——Molecular design, synthesis and inhibitory activity of acrylates (acrylamides)

Molecular modeling of acrylates (acrylamides) with D1 protein of Pisum sativum is presented. Studies show that the binding force mainly includes H-bond interaction, Van der Waals and π-ring stacking interaction. It was found that SER 268 in D1 protein might be an important binding site. It is important for high inhibitory activity of compounds whether an electronegative atom in alkyl of ester linkage could make H-bond interaction with SER 268 in D1 protein. Thus some new acrylates (acrylamides) were designed and synthesized, Bioassay indicated that these new compounds showed expected Hill reaction inhibitory activity.     

Antituberculosis and cytotoxic activities of triorganotin(Ⅳ) complexes

Five triorganotin（Ⅳ）（1-5） complexes of cinnamic acid.（Z）-2-acetamido-3-phenylacrylic acid,3-methylbut-2-enoic acid,and 2,2-diphenylacetic acid have been synthesized and characterized by ¹H-¹³C-¹¹⁹Sn NMR,UV,and IR.The spectroscopic investigation demonstrated that the carboxylate group acts as a monodentate ligand in triorganotin（IV） compounds.Five triorganotin（Ⅳ） complexes were screened against the log phase culture of Mycobacterium tuberculosis H37Rv by colorimetric method using XTT dye as growth indicator.The MICs were found to be 0.08 and 1.25μg/mL.     

Synthesis and magnetism of μ-isophthalato dinuclear lanthanide(Ⅲ) complexes

Seven new μ-isophthalato dinuclear lanthanide(Ⅲ) complexes, namely [Ln2(IPHTA)(Me2-phen)4-(ClO4)2](ClO4)2 (Ln = La, Nd, Sm, Eu, Gd, Ho, Er), where Me2-phen denotes 2,9-dimethyl-1, 10-phenanthroline (Me2-phen) , IPHTA represents isophthalate dianion, have been synthesized and characterized by elemental analyses, molar conductance measurements, IR, ESR and electronic spectra. The variable-temperature magnetic susceptibilities of [Gd2( IPHTA) (Mez-phen)4 (ClO4)2] (ClO4)2 complex were measured in the temperature range of 4-300 K and the observed data were successfully simulated by the equation based on the spin Hamiltonian operator, H = - 2JS1 · S2, giving the exchange parameter J =- 0.19 cm-1 . This result is commensurate with a weak antiferromagnetic spin-exchange interaction between Gd(Ⅲ)-Gd(Ⅲ) ions within the complex.     

Synthesis, characterization and magnetism of μ-chloranilato bi-nuclear chromium (III) complexes

Five new chloranilato-bridged binuclear chromium (III) complexes have been synthesized and identified as [Cr2(CA)L4]-(ClO4)4[L denotes 5-methyl-1,10-phenanthroline (Me-phen); 2,9-dimethyl-1, 10-phenanthroline ( Me2-phen); 5-chloro-1,10-phenanthroline(Cl-phen); diaminoethane (en) or 1,3-diaminopropane (pn)], where CA represents the dianion of chloranilic acid. Based on elemental analyses, molar conductivity and magnetic moment of room-temperature measurements, and IR and electronic spectral studies, it is proposed that these complexes have CA-bridged structures and consist of two chromium (III) ions, each in an octahedral environment. The complexes [Cr2(CA)(Me-phen)4](ClO4)4(1) and [Cr2(CA)(Me2-phen)4](ClO4)4(2) were further characterized by variable temperature (4.2-300 K) magnetic susceptibility measurements and the observed data were successfully simulated by the equation based on the spin Hamiltonian operator, , giving the exchange parameter J = -7.8 cm-1 for (1) and J= -6.5 cm*1 for (2). This result