Synthesis,Characterization and Third-Order Nonlinear Optical Properties of a Series of Ruthenium(II) Complexes Containing 2-Arylimidazo-[4,5- f ][1,10]Phenanthroline

Three novel mononuclear ruthenium(II) complexes [Ru(dmp) 2 L] 2+ [dmp = 2,9-dimethyl-1,10-phenanthroline, L = 2-phenylimidazo-[4,5- f ][1,10]phenanthroline (PIP), 2-(4'-hydroxyphenyl)imidazo-[4,5- f ][1,10]phenanthroline (HOP), 2-(4'-dimethylaminophenyl)imidazo-[4,5- f ][1,10]phenanthroline (DMNP)] were synthesized and characterized by ES-MS, 1 H NMR, UV-Vis and electrochemistry. The nonlinear optical (NLO) properties of the ruthenium(II) complexes were investigated by Z -scan techniques with 12 ns laser pulses at 540 nm, and all of them exhibit both NLO absorption and self-defocusing effects. The corresponding effective NLO susceptibility | h 3 | of the complexes is in the range of 5.15 2 10 m 12 m 6.34 2 10 m 12 esu.     

(N‐{[4‐(1,3‐Benzothiazol‐2‐yl)anilino]carbonylmethyl‐κO}iminodiacetato‐κ3O,N,O′)(1,10‐phenanthroline‐κ2N,N′)cobalt(II) pentahydrate

The title compound, [Co(C₁₉H₁₅N₃O₅S)(C₁₂H₈N₂)]·5H₂O, has a moderately distorted octahedral coordination environment composed of two N atoms of a 1,10‐phenanthroline ligand and one N and three O atoms of an N‐{[4‐(1,3‐benzothiazol‐2‐yl)anilino]carbonylmethyl}iminodiacetate (ZL‐5²⁻) ligand. The ring systems of the phenanthroline and ZL‐5²⁻ ligands are coplanar and the complexes pack in layers parallel to the ab plane with the rings of adjacent complexes facing one another. The layers stack along the c axis and are linked by hydrogen bonds involving the five water solvent molecules in the asymmetric unit and O atoms of the acetate groups of the ZL‐5²⁻ ligand. This is believed to be the first crystal structure of a complex of a 2‐(4‐aminophenyl)benzothiazole ligand.     

超细粉体二硫纶·取代菲咯啉铁(Ⅱ)配合物的光敏性研究

报道了新近合成的二硫纶·取代菲咯啉铁 (Ⅱ )配合物FeLL′(L =mnt2 - ,1 ,2 二氰基乙烯 1 ,2 二硫醇离子 ,L′ =phen 5,6 dione,1 ,1 0 菲咯啉 5,6 二酮 ;5 NO2 phen ,5 硝基 1 ,1 0 菲咯啉 )的电子吸收光谱、电子发射光谱及对CdS的光敏性 ,研究了FeLL′对CdS的光敏化作用与其电子光谱间的关系     

Luminescent Ruthenium(II) Polypyridyl Complexes as Nonviral Carriers for DNA Delivery

Two new luminescent ruthenium(II) polypyridyl complexes, [Ru(bpy)₂(tpt‐phen)]Cl₂ ( 1 ; bpy=2,2′‐bipyridine, tpt‐phen=triptycenyl‐1,10‐phenanthroline) and [Ru(phen)₂(tpt‐phen)]Cl₂ ( 2 ; phen=1,10‐phenanthroline), have been developed as potential nonviral vectors for DNA delivery. Photophysical and electrochemical properties of the complexes have been investigated and corroborated with electronic structure calculations. DNA condensation by these complexes has been investigated by UV/Vis and emission spectroscopy, circular dichroism spectroscopy, atomic force microscopy, dynamic light scattering, confocal microscopy, and electrophoretic mobility studies. These complexes interact with DNA and efficiently condense DNA into globular nanoparticles that are taken up efficiently by HeLa cells. DNA cleavage inability and biocompatibility of complexes have been explored. Both complexes have good gene transfection abilities.     

稀土(La,Ce,Er)-L-亮氨酸-邻菲啰啉三元配合物的合成及其抑菌活性

在乙醇-水介质中,经60℃水浴加热合成了三种稀土固体配合物。对其进行络合滴定、摩尔电导、元素分析、紫外光谱、红外光谱、热重-差热分析等测试,推测其化学组成为[Re(L-leu)3Phen]Cl3.nH2O,并对配合物进行大肠杆菌、金黄色葡萄球菌和枯草芽孢杆菌抑菌性质的测试;结果表明:LaCl3,CeCl3,ErCl3和L-亮氨酸没有抑菌效果,邻菲啰啉与三元稀土配合物对这三种菌都具有抑菌效果,但是三元稀土配合物的抑菌效果明显强于邻菲啰啉,而且对大肠杆菌抑菌效果更好。     

Density functional theory studies on copper phenanthroline complexes

Density functional theory calculations have been employed to investigate the role of structural properties of copper phenanthroline complexes for DNA-cleavage activity. Structural changes imposed on the coordination geometries of Cu(phen)(2)(+,2+) (phen = 1,10-phenanthroline) linked by a serinol bridge (abbreviated as Clip) were studied, as well as their energetic profiles. Our calculations show that structures of these copper complexes (in this work named as clipped complexes) strongly depend on the position of the link, rather than on the copper oxidation state. Ionization energies slightly differ among the three selected complexes, while inner-sphere reorganization energies more markedly depend on the serinol link. However, the relative rates of the redox reaction of Cu(phen)(2), Cu(2-Clip-phen), and Cu(3-Clip-phen) were found not to correlate with their relative DNA-cleavage activity experimentally observed. Thus, the serinol link mainly affects the structural properties of copper phenanthroline complexes rather than their electronic properties. Docking simulations of clipped and nonclipped Cu(I) phenanthroline complexes on a DNA 16mer, d[CGCTCAACTGTGATAC](2), were finally performed to assess how different structural properties could affect the formation of DNA adducts. This analysis revealed that the most stable adducts of Cu(phen)(2+) and Cu(3-Clip-phen)(+) with DNA bind in the minor groove, whereas Cu(2-Clip-phen)(+) binds preferentially into the major groove.     

Antibacterial,SOD mimic and nuclease activities of copper(II) complexes containing ofloxacin and neutral bidentate ligands

Drug‐based mixed‐ligand copper(II) complexes of type [Cu(OFL)(Aⁿ)Cl]·5H₂O (OFL = ofloxacin, A¹ = pyridine‐2‐carbaldehyde, A² = 2,2′‐bipyridylamine, A³ = thiophene‐2‐carbaldehyde, A⁴ = 2,9‐dimethyl‐1,10‐phenanthroline, A⁵ = 2,9‐dimethyl‐4,7‐diphenyl‐1,10‐phenanthroline, A⁶ = 4,5‐diazafluoren‐9‐one, A⁷ = 1,10‐phenanthroline‐5,6‐dione and A⁸ = 5‐nitro‐1,10‐phenanthroline) were synthesized and characterized. Spectral investigations of complexes revealed square pyramidal geometry. Viscosity measurement and absorption titration were employed to determine the mode of binding of complexes with DNA. DNA cleavage study showed better cleaving ability of the complexes compared with metal salt and standard drug by conversion of a supercoiled form of pUC19 DNA to linear via circular. From the SOD mimic study, concentration of complexes ranging from 0.415 to 1.305 µM is enough to inhibit the reduction rate of NBT by 50% (IC₅₀) in the NADH‐PMS system. Antibacterial activity was assayed against selective Gram‐negative and Gram‐positive microorganisms using the doubling dilution technique. Copyright © 2010 John Wiley & Sons, Ltd.     

Thermal properties of cyanatocopper(II) complexes with pyridine,bipyridine and phenanthroline

The thermal properties of cyanatocopper complexes with pyridine, bipyridine and phenanthroline are described in this paper. It was found that the thermal stabilities of the complexes were found to increase in the order pybipy2(NCS)₂ (L=pyridine and its methyl derivates) which are composed of the liberation of ligandsL and redox reactions of thiocyanate ligands with the central Cu(II) atom [1, 2]. The decomposition temperature of thiocyanate ligands depends on the properties of the ligandsL present in the coordination sphere. An analogous course of thermal decomposition was also observed for [Cu(bipy)₂(NCX)](NCX) (X=S or Se) [3]. For the phenanthroline complexes [Cu(phen)₂(NCX)₂] (X=S or Se) the thermal stability was found to increase significantly (by about 140C) and the decomposition stoichiometry was also changed [3].The present paper contains the results of thermoanalytical studies on bipyridine and phenanthroline cyanatocopper complexes, and a comparison of the thermal properties of pyridine cyanato and isothiocyanatocopper complexes.     

Syntheses,Structures and Properties of Four New Transitional Metal Complexes Based on Benzotriazole‐5‐carboxylic Acid

Four new complexes, [Zn(btca)(2,2′‐bpy)] ( 1 ), [Mn(btca)(2,2′‐bpy)] ( 2 ), [Co(btca)(phen)] ( 3 ), and [Cu(btca)(phen)] ( 4 ), (H₂btca=benzotriazole‐5‐carboxylic acid, 2,2′‐bpy=2,2′‐bipyridine, phen=1,10‐phenanthroline), were successfully synthesized and characterized by elemental analysis, single crystal X‐ray diffraction, and IR spectroscopy. Complexes 1 – 4 crystallize in the orthorhombic system with space group of Pbca and show similar 2D layers, which are interlinked to supramolecular networks by π‐π stacking interactions. Furthermore, TGA curves show that complexes 1 – 4 have good thermal stability. Solid‐state fluorescent property of complex 1 was also investigated at room temperature.     

Electrophilic substitution in phenanthroline coordinated to transition metal ions. Rates of nitration of some rhodium(III) and cobalt(III) complexes

Summary The rates of nitration in sulphuric acid of 1,10-phenanthroline coordinated to rhodium(III) and cobalt(Ill) in a number of complexes have been measured and found to be much greater in these complexes than in free phenanthroline under the same conditions. Relative rates are generally higher in those complexes which bear the smaller overall positive charges, but these charges may be modified by protonation of the other ligands in the complexes.Contrary to earlier reports, some other electrophilic substitutions do not occur in a variety of phenanthroline complexes.     

邻菲罗啉-氨基酸铜(Ⅱ)配合物的合成及表征

合成了三种邻菲罗啉（Ｐｈｅｎ）－氨基酸酮（Ⅱ）的配合物：［Ｃｕ（Ｐｈｅｎ）（Ｌ－Ｈｉｓ）］·２ＣｌＯ４·Ｈ２Ｏ,［Ｃｕ（Ｐｈｅｎ）（Ｇｌｙ）］·ＣｌＯ４·Ｈ２Ｏ和［Ｃｕ（Ｐｈｅｎ）（Ｌ－Ｐｒｏ）］·ＣｌＯ４·０．５Ｃ２Ｈ５ＯＨ（Ｌ－Ｈｉｓ：组氨酸;Ｇｌｙ：甘氨酸：Ｌ－Ｐｒｏ：脯氨酸）。用元素分析、摩尔电导、ＩＲ和电子吸收光谱等手段对配合物进行了表征     

Bis(4,4′‐dimethyl‐2,2′‐bipyridine) ruthenium (II) Complexes Containing 2‐Arylimidazo‐ [4,5‐f] [1,10] phenanthroline: Syntheses,Characterization and Third‐order Nonlinear Optical Properties

Four novel mononuclear ruthenium(II) complexes [Ru(dmb)₂L]²⁺ [dmb = 4,4′‐dimethyl‐2,2′‐bipyridine, L = imidazo‐[4,5‐f][1,10]phenanthroline (IP), 2‐phenylimidazo‐[4,5‐f][1,10]phenanthroline (PIP), 2‐(4′‐hydroxyphenyl)imidazo‐[4,5‐f] [1,10] phenanthroline (HOP), 2‐(4′‐dimethylaminophenyl) imidazo‐[4, 5‐f] [1,10] phenanthroline (DMNP)] were synthesized and characterized by ES‐MS, ¹H NMR, UV‐vis and electrochemistry. The nonlinear optical properties of the ruthenium(II) complexes were investigated by Z‐scan techniques with 12 ns laser pulse at 540 nm, and all of them exhibit both nonlinear optical (NLO) absorption and self‐defocusing effect. The corresponding effective NLO susceptibility |x³| of the complexes is in the range of 2.68 × 10^?12‐4.57 × 10^?12 esu.     

Synthesis and spectroscopic characterization of ternary complexes of copper(II) glycylglycine and substituted phenanthrolines

Summary Complexes of Cu(glygly)phen ygly = glycylglycine; phen = 4,7-dimethyl [(1)], 5,6-dimethyl [(2)], 5-NO₂[(3)], 5-Cl[(4)], 2-oxazolinyl (2-ox) [(5)] Phenanthroline and bis(2-oxazolinylphenanthroline)-copper(II) [(6)] were synthesized and characterized by conductivity measurements, e.p.r., i.r. and reflectance electronic spectroscopies.A broad u.v.-vis. band in the 620–640 nm range and a shoulder at ca. 825 nm suggest that these complexes are five-coordinate. The e.p.r. spectra indicate a stronger equatorial ligand field in the ternary complexes which is absent in the binary Cu-phen complexes, suggesting square pyramidal coordination, whose base contains the three donor atoms from glygly (O, N, N) and one donor from the phenanthroline nitrogen atom. The other nitrogen-containing ligand of the phenanthroline is in an apical position.The spectroscopic results can be correlated with electronic and steric effects attributable to the different substituents on the phenanthroline ligands.Only small variations in the structure of the ternary complexes occur as a function of the electronic effects of substituents on the aromatic phenanthroline ring ligands. Steric hindrance predominates in determining coordination geometry around copper(II).     

Synthesis of phenanthroline‐terminated polymers and their Fe(II)‐complexes

Well‐defined mono‐ and bifunctional, phenanthroline‐terminated poly(ethylene glycol) and polyisobutylene capable of polymer network formation were synthesized. The starting materials mono‐ and bi‐phenanthroline‐ (phen) terminated poly(ethylene glycols) (mPEG‐phen, phen‐PEG‐phen) and polyisobutylenes (PIB‐phen, phen‐PIB‐phen) were prepared by the Williamson synthesis and characterized by means of ¹H NMR and MALDI‐TOF mass spectrometry. According to UV–Vis spectrophotometry and ESI‐TOF mass spectrometry, the phenanthroline‐terminated polymers underwent quantitative complex formation with ferrous ions in solution. The aqueous solution of mPEG‐phen shows self‐assembly behavior. Important parameters, such as critical micelle concentration and hydrodynamic radius of the aggregates were also determined. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2709–2715, 2010     

邻香草醛缩丙氨酸盐及邻菲咯啉与Ln(Ⅲ)三元配合物的合成与表征

某些水扬醛类氨基酸的金属配合物具有特殊的性质和应用[1 ,2 ] ,近年来 ,过渡金属离子的此类希夫碱配合物有不少报道。本工作在无水乙醇体系中 ,用稀土硝酸盐与邻香草醛缩丙氨酸钾及邻菲咯啉作用合成了未见文献报道的三种混配配合物 ,并对其组成和配位方式进行了研究。1　实验部分1 1　主要仪器与试剂美国Ｂｉｏ ＲａｄＦＩＳ1 65型红外光谱仪 ,ＫＢｒ压片 ;美国ＰＥ2 4 0 0 (Ⅱ )型元素分析仪 ;岛津ＵＶ 30 0 0双光束分光光度计 ;ＤＤＳ 1 1Ａ型电导率仪 ;德国ＳＴＡ40 9ＺＰ热分析仪。Ｌｎ2 Ｏ3纯度高于 99 9% ;ＤＬ α 丙氨酸为生化试剂…     

Synthesis, structure, and metal complexation behavior of a new type of functionalized chiral phenanthroline derivative

SmI(2) serves as an effective promoter for the coupling of 1,10-phenanthroline with an epoxide to generate a new class of chiral, functionalized ligands that readily form complexes with metals. Structural studies of the resulting phenanthroline derivative and two of its metal complexes are reported.     

Synthesis,Characterization, Antibacterial and Antifungal Activity of Yttrium(III) Complexes Including 1,10‐Phenanthroline

Two rare metal coordination complexes of yttrium(III) including 1,10‐phenanthroline, Y(phen)₂(NO₃)₃ and (phenH)₂[Y₂(pydc)₃(NO₃)₂·6H₂O] (phen=1,10‐phenanthroline, pydc=2,6‐pyridinedicarboxylate), and a proton transfer compound (phenH⁺)₂(pydc^2?) were synthesized and characterized by elemental analysis, molar conductance, infrared spectra (IR), nuclear magnetic resonance (NMR) and thermal analysis. The proposed structures of yttrium complexes were exhibited. The in vitro biological activities of the newly synthesized complexes have also been investigated against Bacillus coli, Staphylococcus aureus and Candida albicans. The results showed that yttrium(III) complexes including 1,10‐phenanthroline exhibited better antibacterial/antifungal activity than their ligands and corresponding compounds.     

Study of Anti-Apoptotic mechanism of Ruthenium (II)Polypyridyl Complexes via RT-PCR and DNA binding

A set of novel mononuclear polypyridyl complexes of Ru (II) with N – N donar ligands 1, 10 phenanthroline (phen), 2, 2′ bipyridine (bpy), 4, 4′-dimethyl 2, 2′ bipyridine (dmb) and an intercalating ligand (bnpip = 2-(4-butoxy-3-nitrophenyl)-1H-imidazo [4,5-f] [1,10] phenanthroline) have been synthesized and characterized by various spectral methods. The RT - PCR assays suggest that ruthenium (II) complexes inhibit MCF-7, breast cancer cell line by inducing apoptosis via inhibition of cell cycle check points cyclin D, cyclin E and also upregulation of caspase 8 (protein involved in late Apoptosis). Further the binding potency of Ru (II) complexes were investigated using various spectroscopic techniques like UV–visible, fluorescence and viscosity studies. The complex binds to DNA in an intercalative mode as confirmed by viscosity data with differential binding strength. All complexes show cleavage of the pBR322 DNA through a singlet oxygen production. Theoretical evidence via docking of the complex with DNA reveals the significant residues of binding as guanine.     

Ln(Ⅲ)与2-羟基-1-萘醛缩蛋氨酸盐及邻菲咯啉三元配合物的合成与表征

合成了稀土硝酸盐与希夫碱盐2-羟基-1-萘醛缩蛋氨酸钾(以KL表示)及邻菲咯啉(Phen)的四种固体三元配合物。通过元素分析，IR，UV，DTA-TG及摩尔电导分析等手段确定配合物的组成为[Ln(L)(Phen)(NO3)(H2O)]NO3(Ln＝Gd，Dy，Er，Yb)，并对它们的配合方式及某些物理和化学性质进行了研究。