手性二噁唑啉吡啶铁和镍配合物的制备与表征

Tridentate bis(oxazolinylpyridine)(1) reacted with nickel chloride or ferrous chloride in anhydrous ethanol to form bis(oxazolinylpyridine) Nickel(Ⅱ) and Iron(Ⅱ) complexes. The stable solid complexes were characterized with IR， UV， MS， XPS and elemental analysis. No stable complexes were formed with bidentate bis(oxazoline)(2) ins- tead of bis(oxazolinylpyridine).     

Syntheses and photophysical properties of visible-light-absorbing Ru(II) polypyridyl complexes possessing (pyridylpyrazolyl)metal tethers

Novel Ru(II) polypyridyl complexes possessing pyridylpyrazolyl tethers were synthesized. Reactions with various organometallic precursors readily afforded multinuclear complexes which possess a light-harvesting Ru(II) core and (pyridylpyrazolyl)metal fragments in high yields. Analysis of the photophysical properties of the obtained multinuclear complexes revealed that the complexes had similar absorption and emission characteristics; however, their emission quantum yields decreased in proportion to the number of metal fragments. The di- and trinuclear complexes were stable under donating solvent such as CH₃CN.     

Electron transfer reactions of nickel(III) and nickel(IV) complexes

This review narrates the electron transfer reactions of various nickel(III) and nickel(IV) complexes reported during the period 1981 until today. The reactions have been categorized mainly with respect to the type of nickel complexes. The reactivity of nickel(III) complexes of macrocycles, 2,2′-bipyridyl and 1,10-phenanthroline, peptides and oxime–imine, and of nickel(IV) complexes derived from oxime–imine, oxime and miscellaneous ligands with various organic and inorganic electron donors have been included. Kinetic and mechanistic features associated with such interactions have been duly analyzed. The relevance of Marcus cross-relation equations in the delineation of the electron transfer paths has also been critically discussed.     

Synthesis,structure, spectroscopic,and DNA binding properties of Co(III) and Ni(II) complexes with ((E)-2-(amino((pyridin-2-ylmethylene)amino)methylene)maleonitrile)

Two new complexes, [Co(L)₂]Cl·(MeOH)₂ (1) and [Ni(L)₂]₄·EtOH (2) (L?=?(E)-2-(amino((pyridin-2-ylmethylene)amino)methylene)maleonitrile), were synthesized and characterized by X-ray crystallography, IR, UV, and fluorescence spectroscopy. According to X-ray crystallographic studies, each metal was six-coordinate with six nitrogens from two ligands. Both complexes form two-dimensional supramolecular networks via hydrogen bonding and π–π interactions. Ultraviolet and visible spectra showed that absorptions arise from π–π ^?, MLCT, and d–d electron transitions. Fluorescence spectroscopy revealed moderate intercalative binding of these two complexes with EB–DNA, with apparent binding constant (K _app) values of 9.14?×?10⁵ and 3.20?×?10^5?M^?1 for Co(III) and Ni(II) complexes, respectively. UV–visible absorption spectra showed that the absorption of DNA at 260?nm was quenched for 2 but quenched then improved for 1 with addition of complexes, tentatively attributed to the effect of the combined intercalative binding and electrostatic interaction for 1.     

Photoluminescence studies of iodobis-(tricyclohexylphosphine)copper(I) and iodobis-(tricyclohexylphosphine)copper(I) benzene solvate

Two newly prepared complexes were found to exhibit strong solid state emission behavior. The complexes are iodobis-(tricyclohexylphosphine)copper(I) and iodobis-(tricyclohexylphosphine)copper(I) benzene solvate. To understand the emission behavior of these complexes, density functional theory (DFT) calculations were employed. These calculations allowed the identification of major atomic contributions to HOMO, LUMO and LUMO+n orbitals. The excitation mechanism was found to be a combination of ligand to metal charge transfer (LMCT) and metal to ligand charge transfer (MLCT), with the dominance of the former. The emission lifetimes were also investigated and the decays of the complexes were found to be a bi-exponential in both methanol and cyclohexane.     

含铋（Ⅲ）配合物的合成及其铋的配位性质

由于金属铋的绿色安全性，其配合物的应用领域不断扩大。因此，从分子水平探索配合物结构具有十分重要的意义。本文主要根据有机配体的不同，对三价铋离子配合物的合成及相应的结构进行分类概括，并针对固态铋配合物，对铋(Ⅲ)离子在各配合物中所处的配位环境以及与配体的配位方式等进行了综述。     

三价金配合物抗肿瘤活性研究*

三价金配合物具有潜在的抗肿瘤活性,是目前金属药物领域的研究热点。本文按配位原子的不同总结了稳定三价金配合物的结构特征,按其生物活性的构效关系、生物靶点和作用机制综述了三价金配合物抗肿瘤活性研究的最新成果：配体的结构特点以及离去基团对三价金配合物的体外细胞毒性影响较大;介绍了用于检测三价金配合物与可能的生物靶分子之间的相互作用的多种物理和生物学方法,重点关注了相互作用的模式,如嵌入/静电吸引/共价结合等,并解释了三价金配合物抗肿瘤活性的原因。最后提出了一些研究新思路,以期有助于设计得到靶标明确的具有良好药理活性的抗肿瘤药物。     

Comparative study on the photophysical properties between carbene-based Fe (II) and Ru (II) complexes

The comparative study on the photophysical properties between cheap metal Fe (II) complexes and noble metal Ru (II) complexes with identical ligand coordination is performed by the combination of density functional theory (DFT) and time-dependent density functional theory (TDDFT) to evaluate the potential alternative applications of Fe (II) complexes. RuBIP (BIP = 2,6-bis (imidazol-2- ylidene)pyridine) is theoretically established that the radiative lifetime of the second lowest triplet state is more consistence with experimental value. However, FeBIP retains nonluminous because of low-lying ³MC originated from weak d orbital splitting. FeBIPC (FeBIP with carboxylic acid groups) has twice longer lifetime than its parent complex FeBIP due to the great decrease of the energy gap between ³MLCT and ³MC. What's more, the lifetimes of Fe (II) complexes detected in the experiments are more accessible to nonradiative decay lifetimes of ³MC. The carboxylic acid groups are beneficial for the improvement of luminescent possibility and controllability of Fe (II) complexes, while there is still a huge challenge for effective material replacement comparing with Ru (II) complexes.     

Synthesis, Crystal Structure, UV-vis and EPR Studies of（ NH3CH2CH2NH2 ） 2.5 [ Mo0.5^（V）W0.5^（VI）O2 （ OC6H4O ） 2]

Cis-dioxo-metal complex ( NH3CH2CH2NH2 ) 2.5 [ Mo0.5^(V)W0.5^(VI)O2 ( OC6H4O ) 2] 1 was obtained by the reaction of tetra-butyl ammonium hexamolybdotungstate with 1, 2-dihydroxybenzene in the mixed solvent of CH3OH, CH3CN and ethylenediamine,and characterized by X-ray diffraction, UV-vis and EPR analysis. Compared with its analogous complexes (NH3CH2CH2NH2)3[Mo^(V)O2(OC6H40)2] 2 and (NH3CH2CH2NH2)2[W^(VI)O2(OC6H4O)2] 3, the results show that tungsten(VI) is less active in redox than molybdenum (VI) and that the change of the valence induced by substitution of W(VI) for Mo(V) in EMO2(OC6H40)2]n- does not influence the coordination geometry of the complex anion in which the metal center exhibits distorted octahedral coordination with cis-dioxo catechol. The responses to EPR of complexes 1 and 2 are active but complex 3 is silent,and the UV-vis spectra exhibited by the three complexes are obvious different because of the different electronic configuration between the central Mo(V) and W(VI) ions in the complexes.It is noteworthy that complexes 1 and 2 have the similar EPR signal to flavoenzyme, suggesting that the three complexes have the same coordination geometry feature with the co-factor of flavoenzyme.     

含双二苯基膦甲烷铜(Ⅰ)配合物的研究进展

本文概述了含双二苯基膦甲烷铜(Ⅰ)配合物的化学进展,总结了配合物的合成方法:置换法、还原法、电化学方法和直接加成法,全面论述了双核、三核、多核和异核配合物的结构特征,探讨了该类配合物的重要荧光性质。     

Sulfur-Bonded Coordination Compounds of Palladium(II) and Platinum(II) and Their Antimicrobial Activity

The synthetic, spectroscopic, and biological studies of some new palladium(II) and platinum(II) complexes derived from biologically active sulfur donor ligands 1H-indol-2,3-dione benzothiazoline (Bzt ₁ H) and 5-nitro-1H-indol-2,3-dione benzothiazoline (Bzt ₂ H) have been described. The reactions were carried out in 1:2 molar ratios. The authenticity of the benzothiazolines and their complexes has been established on the basis of elemental analyses; molecular weight determinations; and IR, ¹ H NMR, ¹³ C NMR, and UV spectral studies. Based on IR and ¹ H NMR spectral studies, a square-planar structure has been assigned to these complexes. Studies were conducted to assess the comparative growth inhibiting potential of the synthesized complexes against the benzothiazolines for a variety of fungal and bacterial strains. The studies demonstrate that the ligands and complexes possess antimicrobial properties. Further, it was noted that the growth-inhibiting potential of the complexes is greater than the parent benzothiazolines.     

Spectral and photophysical properties of mono and dinuclear Pt(II) and Pd(II) complexes: An unusual emission behaviour

Eight mononuclear complexes of the formula [M(N-N)(DHB)] and two binuclear complexes of the formula [M₂(BPY)₂(THB)] where M = Pd(II) or Pt(II), N-N = 2,2′-bipyridine (BPY), 2,2′-biquinoline (BIQ), 4,7-diphenyl-1,10-phenanthroline (DPP), 1,10-phenanthroline (PHEN); DHB = dianion of 3,4-dihydroxybenzaldehyde and THB = tetraanion of 3,3′,4,4′-tetrahydroxy benzaldazine were prepared and their electrochemical, spectral and photophysical properties were examined. These complexes were characterized by chemical analysis, IR and proton NMR spectroscopy. A detailed study on the absorption spectroscopy of these complexes was made. These complexes were found to show a low-energy solvatochromic ligand-to-ligand charge-transfer (LLCT) band. The electronic energies of these bands have been analyzed and compared with electrochemical data. Emission behaviour of the complexes of the series, [Pt(N-N)(DHB)], [Pt(N-N)(DHBA)] where DHBA is the dianion of 3,4-dihydroxybenzoic acid and [Pt₂(BPY)₂(THB)] was also investigated. These platinum complexes were found to emit from a low-energy state at low temperature and a high-energy state at room temperature. Photophysics of these complexes is also discussed.     

Synthesis,characterization and antimicrobial activity of pentagonal-bipyramidal isothiocyanato Co(II) and Ni(II) complexes with 2,6-diacetylpyridine bis(trimethylammoniumacetohydrazone)

Pentagonal-bipyramidal isothiocyanato Co(II) and Ni(II) complexes with condensation product of 2,6-diacetylpyridine and trimethylammoniumacetohydrazide (Girard’s T reagent) were synthesized and characterized by elemental analyses, IR and UV–vis spectra, molar conductivity, and magnetic susceptibility. Crystal structures of the Co(II) and Ni(II) complexes were also determined. Antimicrobial activities of the ligand and metal complexes were examined.     

Cationic complexes of Eu(III) and Sr(II) with diphosphine dioxides in organic extracts

IR spectroscopy was used to study the structure and composition of Eu(III) and Sr(II) complexes formed by cation-exchange extraction of these metals from their aqueous nitrate solutions with dichlorethane solutions of mixtures of chlorinated cobalt(III) dicarbollide (CCD) as a superacid with diphenyldiphosphine dioxides containing a methyl (Me-DPDO), ethyl (Et-DPDO), or polyoxyethylene bridge between two phosphorus atoms of phosphine oxide groups. At molar ratios DPDO/CCD ≤ 1, [Eu(H₂O)_nL₄]³⁺ complexes are formed in organic phases, whereas with an excess of DPDO relative to CCD, Eu(NO₃)L ₄ ²⁺ complexes are formed, where L = Me-or Et-DPDO. Polyoxyethylenediphosphine dioxide forms anhydrous complexes of composition Eu:L = 1:1 and 1:2 with Eu(III) and outer-spheric complexes of composition Sr:L = 1:1 and 1:2 with Sr(II), where the organic ligand molecules envelop the hydrated Sr(H₂O) _n ²⁺ cation. The peculiarities of extraction of the complexes are explained based on data about their composition and structure.     

Physicochemical Investigation on the Complexes of Co(II), Ni(II) and Cu(II) with Aminocyclodiphosph(V)azane Derivative

Co(II), Ni(II), and Cu(II) form 2:1 complexes with aminocyclodiphosph(V)azane derivative. The complexes have been investigated in solution by the spectrophometric molar ratio and conductometeric methods. The ligand and its complexes have been isolated in solid state and characterized on the basis of microanalytical, infrared, electronic, magnetic moment, 1 H NMR and mass spectral data. The cobalt and nickel complexes were assigned to be in tetrahedral structure while the copper complex is assigned to be in square planar.     

Folate receptor-mediated gene delivery using folate-poly(ethylene glycol)-poly(L-lysine) conjugate

For efficient receptor-mediated gene transfection, a new and simple formulation method based on using PEI and FOLPEGPLL conjugate was presented. Luciferase plasmid DNA and PEI were complexed to form slightly positive-charged nanoparticles, onto which FOL-PEG-PLL conjugate was surface coated. With increasing the coating amount of FOL-PEG-PLL conjugate, the FOL-PEG-PLL/PEI/DNA complexes exhibited increased surface zeta-potential values with concomitantly increased diameters, indicating that the PLL part was physically anchored on the surface of preformed PEI/DNA complexes with FOL moieties being exposed on the outside. The formulated complexes exhibited a considerably higher transfection efficiency against FOL receptor over-expressing KB cells than FOL receptor deficient A549 cells. This was caused by an enhanced cellular uptake of the resultant complexes via a receptor-mediated endocytosis process. The formulated complexes showed a higher gene expression level, even in the presence of serum, than the PEI/DNA or Lipofectamine/DNA complexes. This was attributed to the PEG chains present on the surface of complexes that could work as a protective shield layer against aggregation caused by non-specific protein adsorption. The FOL-PEG-PLL/PEI/DNA complexes also demonstrated better cell viability than the PEI/DNA complexes.(1)H NMR spectrum of FOL-PEG-PLL conjugate.     

Copper(I) and silver(I) complexes of bridging bis(quinaldinyl)phenylphosphine oxide ligand

Abstract

A novel tertiary phosphine oxide containing two quinaldinyl substituents has been synthesized according to adapted literature procedures. Its coordination properties toward Cu(I) and Ag(I) were investigated and the resulting complexes were analyzed by single crystal X-ray diffraction. Multinuclear complexes are formed, wherein the ligand is bridging across two metal centers. Though for the silver complex, no argentophilic interactions are present. The copper complex was characterized further by multinuclear NMR spectroscopy at variable temperatures.     

Thermogravimetric and spectroscopic studies on La(III) and Ce(III) complexes with some thio-schiff bases

Solid complexes of five derivatives of thio-Schiff bases with La(III) and Ce(III) ions were prepared and characterized by elemental and thermogravimetric analyses. The suggested general formula of the solid complexes is [ML₂(H₂O)X]·2H₂O, whereM=trivalent lanthanide ion,L=Schiff base andX=Cl^? or ClO ₄ ^? . Information about the water of hydration, the coordinated water molecules, the coordination chemistry and the thermal stability of these complexes was obtained and is discussed. Additionally, a general scheme of thermal decomposition of the lanthanide-Schiff base complexes is proposed.     

TG,DTA and electrical conductance properties of some Cu(II) AND Mn(II) bisazo- dianils complexes

The TG and DTA of a new series of Mn(II) and Cu(II) complexes with a number of newly prepared bisazo-dianil ligands were studied in the temperature range (20-700°C). The TG and DTG curves display to main steps, the first one within the temperature range (25-330°C) correspond to the elimination of water or and ethanol from the complexes. The second step within the range (350-625°C) is due to the decomposition of the complexes yielding the metal oxides as the final product. The rate constants of the dehydration and decomposition reactions were determined, from which some kinetic parameters were evaluated. The DTA curves show that the dehydration of the metal complexes is an endothermic reaction. In all cases the anhydrous metal complexes undergo exothermic decomposition reactions to give the metal oxide. The thermodynamic parameters (ΔE, ΔH, ΔS, ΔG) for the occurring processes are calculated. The electrical conductivities of the solid complexes were measured and the activation energy of the complex and its free ligand are also calculated. This revised version was published online in August 2006 with corrections to the Cover Date.     

Flash photolysis studies of charge-transfer photochemistry of nickel(II) and cobalt(III) complexes

The photochemical behavior of cobalt(III) and nickel(II) complexes on excitation in the charge-transfer bands is reviewed in this article with particular reference to the study of intermediates. Investigations on the photoredox reactions of cobalt(III) and nickel(II) complexes using flash kinetic spectroscopic methods reveal details on the characteristics of the intermediates produced from the charge-transfer excited states of these metal complexes. The reactive species produced on photolysis of cobalt(III)-amine complexes activate molecular oxygen, producing mononuclear and dinuclear dioxygen species coordinated as superoxo and peroxo forms. Cobalt(III)-amino-acid complexes on photolysis lead to the formation of cobalt(III)-alkyl complexes which are identified as transients. The spectra and the decay kinetics are described with the view to elucidate mechanistic details. Nickel(II) macrocyclic complexes on excitation in the charge-transfer bands lead to oxidation of the metal centre. Scavenging experiments using dioxygen, alcohols and acids were carried out to understand the mechanistic details.