Preparation of photoluminescent compounds of Eu(III), Sm(III), and Dy(III) containing anions of tetrafluoroterephthalic acid

The Ln₂(H₂O)₄(L)₃·2H₂O and Ln₂(phen)₂(L)₃·2H₂O complexes [Ln = Eu(III), Sm(III), or Dy(III); H₂L = C₆F₄(COOH)₂, phen = 1,10-phenanthroline] have been prepared. Structures of the prepared compounds have been confirmed by X-ray diffraction and IR spectroscopy studies. The complexes of Eu(III) have exhibited red photoluminescence stronger than that of the complexes of Sm(III) and Dy(III).     

Thermal studies on metal complexes of 5-nitroso-pyrimidine derivatives

The following Zn(II) complexes of deprotonated 6-amino-5-nitrosouracil (AH), 6-amino-3-methyl-5-nitrosouracil (BH) and 6-amino-1-methyl-5-nitrosouracil (CH) have been prepared and their thermal behaviour studied by TG and DSC techniques: ZnA₂(H₂O)₂, ZnB₂ · 4 H₂O, ZnC₂ · 4 H₂O and ZnC₂(H₂O)₂ · H₂O. The values of the dehydration enthalpy of the complexes are in the 31.3–76.5 kJ mol^?1 H₂O range and, except in the first complex, the dehydration processes take place in several steps. The pyrolysis of the complexes finishes between 540 and 725° C ZnO remaining as residue.     

Metal complexes of tetradentate azo-dye ligand derived from 4,4′-oxydianiline: Preparation,structural investigation,biological evaluation and MOE studies

The Cr (III), Mn (II), Fe (III), Co (II), Ni (II), Cu (II) and Cd (II) complexes were prepared by reaction of its metal chlorides with new azo-dye ligand (H₂L). The ligand derived from 4,4′-oxydianiline and 2-amino-4-chlorophenol was synthesized in a 1:2 molar ratio. The structure of the ligand and its metal complexes was investigated using different tools such as elemental analysis (C, H, N and M), molar conductivity, IR, UV–vis, ¹H-NMR, mass spectrometry and thermogravimetric and differential thermogravimetric studies. The data showed that the ligand acted as a N,N,O,O-binegative tetradentate ligand. All metal complexes had a octahedral structure as depicted by spectral and elemental analyses. The conductivity data showed the electrolytic nature of the Cr (III) and Fe (III) complexes while the other complexes were nonelectrolytes. Thermal analysis studies showed the decomposition of the complexes in four to five steps with the weight loss of hydrated water in the first decomposition step followed by the coordinated water and ligand molecules. Biological activity was tested for the prepared compounds against four bacterial species (Bacillus subtilis, Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa) and against two fungal species (Aspergillus fumigatus and Candida albicans). Also, all complexes were screened for anticancer activities against a breast cancer (MCF-7) cell line. The [Co(L)(H₂O)₂] complex showed the lowest IC₅₀ value. Molecular docking is a key tool in computer drug design. Therefore, investigation of protein receptors and ligand interaction plays a vital role in the design of structurally based drugs. As a result, docking studies were investigated for H₂L ligand, [Mn(L)(H₂O)₂] and [Ni(L)(H₂O)₂] complexes with 5KBC, 3V7B and 4G9M receptors.     

Thermal dehydrations

The behaviour of thermal dehydrations of isomorphous complexes of calcium copper acetate hexahydrate, CaCu(CH₃CO₂)₄·6H₂O and calcium cadmium acetate hexahydrate, CaCd(CH₃CO₂)₄· 6H₂O was studied by means of thermal analyses and X-ray structural analysis. The enthalpy changes for the dehydration of CaCu(CH₃CO₂)₄·6H₂O and CaCd(CH₃CO₂)₄·6H₂O were 315±9.7 and 295±8.0 kJ mol^–1, respectively. The DSC curves of the dehydrations indicated that the seemingly simple dehydrations are more complex than they appear at first sight. Apparent activation energies for the dehydrations of CaCu(CH₃CO₂)₄·6H₂O and CaCd(CH₃CO₂)₄·6H₂O were 85.7±7.4 and 87.9±12.5 kJ mol^–1, respectively.The authors wish to express their thanks to Associate Professor Yasuhiko Yukawa of the Niigata University for the analysis of the X-ray-intensity data.     

Synthesis and some properties of light lanthanide complexes with 4,4′-bipyridine and dibromoacetates

In this study, new complexes with formulae: Ce(4-bpy)(CHBr₂COO)₃·H₂O, Ln(4-bpy)_0.5(CHBr₂COO)₃·2H₂O (where Ln(III) = Pr, Nd, Sm; 4-bpy = 4,4′-bipyridine) and Eu(4-bpy)(CHBr₂COO)₃·2H₂O were prepared, and characterized by chemical and elemental analyses, and IR spectroscopy. The way of metal–ligand coordination was discussed. They are small crystalline. The complexes of Pr(III), Nd(III), and Sm(III) are isostructural in group. Conductivity studies (in methanol, dimethylformamide, and dimethylsulfoxide) were also performed and described. The thermal properties of complexes in the solid state were studied using TG–DTG techniques under dynamic flow of air atmosphere. TG–MS system was used to analyze principal volatile thermal decomposition and fragmentation products evolved during pyrolyses of Ce(III) and Sm(III) complexes in dynamic flow of air atmosphere.     

Synthesis,spectral, thermal,solid state d.c. electrical conductivity,fluorescence and biological studies of lanthanum(III) and thorium(IV) complexes of 24-membered macrocyclic triazoles

A series of La(III) and Th(IV) complexes have been synthesized by template condensation of 2,6-diformyl-4-methylphenol, bis-(4-amino-5-mercapto-1,2,4-triazol-3-yl)alkanes and La(NO₃)₃ ·?6H₂O/Th(NO₃)₄ ·?5H₂O in 2 : 2 : 1 molar ratio in ethanol. These complexes were characterized by elemental analyses, magnetic susceptibility, molar conductance, spectral (IR, UV–Vis, ¹H-NMR, FAB-mass), thermal, fluorescence and solid state d.c. electrical conductivity studies. The complexes are insoluble in water but soluble in DMF and DMSO. The observed molar conductance values indicate non electrolytes. Elemental analyses suggest 1 : 1 stoichiometry, [La(L^I–IV)(NO₃)(H₂O)₂] ·?3H₂O and [Th(L^I–IV)(NO₃)₂(H₂O)₂] ·?3H₂O. Spectroscopic studies indicate that coordination occurs through phenolic oxygen after deprotonation, nitrogen of azomethine group and bridging bidentate nitrates. The solid state d.c. electrical conductivity indicates semiconducting nature. All the Schiff bases and their La(III) and Th(IV) complexes were evaluated for biological properties; some compounds show promising results.     

Synthesis,spectral, crystallography and thermal investigations of novel Schiff base complexes of manganese (III) derived from heterocyclic β-diketone with aromatic and aliphatic diamine

The Schiff base tetradentate ligands N,N-bis-(3,5-dimethyl-1-p-tolyl-1H-pyrazol-4-ylmethylene)-ethane-1,2-diamine (H₂L¹), N,N-bis-(3,5-dimethyl-1-p-sulfonyl-1H-pyrazol-4-ylmethylene)-ethane-1,2-diamine (H₂L²), N,N-bis-(3,5-dimethyl-1-p-tolyl-1H-pyrazol-4-ylmethylene)-benzene-1,2-diamine (H₂L³) and N,N-bis-(3,5-dimethyl-1-p-sulfonyl-1H-pyrazol-4-ylmethylene)-benzene-1,2-diamine (H₂L⁴) were prepared from the reaction between 5-oxo-3-methyl-1-p-tolyl-1H-pyrazole-4-carbaldehyde or 4-(4-formyl-5-oxo-3-methyl-pyrazol-1-yl)-benzenesulfonic acid and o-phenylenediamine or ethylenediamine. And these are characterized by elemental analysis, FT-IR, ¹H NMR and GC–MS. The corresponding Schiff base complexes of Mn(III) were prepared by condensation of [Mn₃(μ₃-O)(OAc)₆(H₂O)₃]·3H₂O with ligands H₂L¹, H₂L², H₂L³ and H₂L⁴. All these complexes have been characterized by elemental analysis, magnetic susceptibility, X-ray crystallography, conductometry measurement, FT-IR, electronic spectra and mass (FAB) spectrometry. Thermal behaviour of the complexes has been studied by TGA, DTA and DSC. Electronic spectra and magnetic susceptibility measurements indicate octahedral stereochemistry of manganese (III) complexes, while non-electrolytic behaviour complexes indicate the absence of counter ion.     

Spectral and thermal investigation of rare earth element 4-methoxy-2-methylbenzoates

4-Methoxy-2-methylbenzoates of Y(III) and lanthanides(III) (La-Lu) were prepared as crystalline anhydrous complexes with general formula Ln(C₉H₉O₃)₃ (complexes of La and Pr as monohydrates). Monohydrates heated in air lose crystallization water molecule and then anhydrous complexes decompose directly to oxides. Only La(III) complex decomposes to oxide with intermediate formation La₂O₂CO₃. The carboxylate group in the studied complexes is a tridentate chelating - bridging or bidentate chelating (Y). This revised version was published online in August 2006 with corrections to the Cover Date.     

Studies on thermal decomposition of 3-chlorobenzoates of rare earth elements in air atmosphere

The conditions of thermal decomposition of the 3-chlorobenzoates of Y, La and the lanthanides from Ce(III) to Lu have been studied. The complexes of La, Pr(III), Sm, Eu, Gd, Tb(III) and Dy were prepared as heptahydrates, those of Ce(III) and Y as pentahydrates, that of Nd as the tetrahydrate, that of Ho as the dihydrate and those of Er, Tm, Yb and Lu as anhydrous salts. On heating, these complexes decompose in three or two stages. They first lose some water molecules and then decompose to oxides through the intermediate formation of LnOCl. Cerium(III) 3-chlorobenzoate loses its crystallization water in two stages and yields the anhydrous salt, which is then transformed directly into CeO₂. All these complexes melt before decomposition in the temperature range 441–513 K.     

Solvation of iron and chromium complexes in alcohol–water mixtures

Solubilities are reported for the perchlorates of five iron(II)-diimine complexes in t-BuOH–H₂O and one in MeOH–H₂O mixtures, for three iron(III)-3-hydroxy-4-pyranonate and three iron(III)-3-hydroxy-4-pyridinonate complexes in MeOH–H₂O and t-BuOH–H₂O, and for two chromium(III)-3-hydroxy-4-pyranonate complexes in MeOH–H₂O. Transfer chemical potentials are thence derived for the various iron(II), iron(III) and chromium(III) complexes, for transfer from H₂O into the respective mixed solvents (at 298.2 K). These results are combined with values reported earlier for related complexes, and for other alcohol–H₂O mixtures, to give an overall picture of solvation, expressed in the thermodynamic format of transfer chemical potentials, for iron(II)-diimine, iron(III)-3-hydroxy-4-pyridinonate and chromium(III)-3-hydroxy-4-pyranonate complexes in H₂O-rich aqueous-alcohol mixtures. Some spectroscopic (¹H-n.m.r.; i.r.) and kinetic (aquation rate constants at 298.2 K) data are reported for the chromium(III) complexes.     

Synthesis, spectral characterization, biological and fluorescence studies of lanthanum(III) complexes with 3-substituted-4-amino-5-hydrazino-1,2,4-triazole Schiff bases

Some lanthanum(III) complexes have been synthesized by reacting lanthanum(III) nitrate with Schiff bases derived from 3-substituted-4-amino-5-hydrazino-1,2,4-triazole and substituted salicylaldehydes. All these complexes are soluble in DMF and DMSO and the low molar conductance values observed indicates that they are non-electrolytes. Elemental analyses suggest the complexes have 1:1 stoichiometry of the type La · L · NO₃ · H₂O, and they were characterized further by spectral and thermogravimetric methods. Fluorescence spectra of one of the representative Schiff bases (II) and its lanthanum(III) complex were investigated in various solvents; the complexes were evaluated for their biological activity.     

Thermogravimetric and spectroscopic characterization of trivalent lanthanide chelates with some schiff bases

Solid complexes of two derivatives of Schiff bases SAT and SAZ with Pr(III), Nd(III), Gd(III), Dy(III), Ho(III), Er(III) and Yb(III) were prepared and characterized by elemental analysis , IR spectra and TG. The suggested formula of the obtained solid complexes is [MLCl₂(H₂O)n] for sat and [MLCl (H₂O)n] for SAZ where M=trivalent lanthanide ion, L=deprotonated ligand and n=2-3. The TG gives information about the coordinated water molecules, thermal stability and the coordination number of M which was found to be 6–8. A scheme of thermal decomposition of the complexes is also proposed. Comparison of the IR spectra of the ligands with those of their complexes indicate the center of chelation in SAT and SAZ which act as tridentate ligands. This revised version was published online in July 2006 with corrections to the Cover Date.     

Synthesis and characterization of azo-linked Schiff bases and their nickel(II), copper(II), and zinc(II) complexes

Azo compounds were prepared by coupling of benzenediazonium chloride ions with 1-amino-2-hydroxy-4-naphthalene sulfonic acid under alkaline conditions, and Schiff bases, L_1–3 were then obtained by the condensation of 1-amino-2-hydroxy-3-(phenylazo)-4-naphthalene sulfonic acid, 1-amino-2-hydroxy-3-(4-ethylphenylazo)-4-naphthalene sulfonic acid, and 1-amino-2-hydroxy-3-(4-nitrophenylazo)-4-naphthalene sulfonic acid with salicylaldehyde. New copper(II), nickel(II), and zinc(II) complexes of the Schiff base ligands were also prepared and characterized by spectroscopic methods, magnetic measurements, elemental, and thermogravimetric analysis.     

Synthesis,Characterization, Antimicrobial Activities,and Structural Studies of Lanthanide (III) Complexes with 1-(4-Chlorophenyl)-3-(4-fluoro/hydroxyphenyl)prop-2-en-1-thiosemicarbazone

Twelve coordinate lanthanide (III) complexes with the general composition [Ln L₃X_n(H₂O)_n] where Ln = Pr(III), Sm(III), Eu (III), Gd (III), Tb (III), Dy (III), X = Cl^?1, NO₃ ^?2, n = 2–7, and L is 1-(4-chlorophenyl)-3-(4-fluoro/hydroxyphenyl)prop-2-en-1- thiosemicarbazone have been prepared. The lanthanide complexes (5) were derived from the reaction between 1-(4-chlorophenyl)-3-(4-fluoro/hydroxyphenyl)prop-2-en-1-thiosemicarbazone (4) with an aqueous solution of lanthanide salt. Chalcone thiosemicarbazone ligand (4) was prepared by the reaction of [1-(4-chlorophenyl)-3-(4-fluoro/hydroxyphenyl)]prop-2-enone (chalcone) (3) with thiosemicarbazide in the presence of hot ethanol. All the lanthanide-ligand 1:3 complexes have been isolated in the solid state, are stable in air, and characterized on the basis of their elemental and spectral data.

Thiosemicarbazone ligands behave as bidentate ligands by coordinating through the sulfur of the isocyanide group and nitrogen of the cyanide residue. The probable structure for all the lanthanide complexes is also proposed. The chalcone thiosemicarbazone ligands and their lanthanide complexes have been screened for their antifungal and antibacterial studies. Some of the synthesized lanthanide complexes have shown enhanced activity compared with that of the free ligand.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Spectral and thermal studies of Y(III) and heavy lanthanide 4-chlorophthalates

Summary Complexes of heavy lanthanide(III) (Gd-Lu) and Y(III) with 4-chlorophthalic acid were prepared and their IR spectra, solubility in water at 295 K and thermal decomposition were investigated. When heated the complexes with general formula Ln₂[ClC₆H₃(CO₂)₂]₃·nH₂O where n=6 for Tb, Dy(III), n=4 for Gd, Ho and Er(III), n=2 for Tm-Lu(III) and n=3 for Y(III) decompose to the oxides Ln₂O₃, Tb₄O₇ with intermediate formation of oxochlorides LnOCl.     

Transition Metal Complexes with Pyrazole-Based Ligands 7. Zn(II), Co(II), Mn(II) and Cu(II) complexes with 3-amino-5-methylpyrazole

Complexes represented by the general formula [MCl₂L₂] (M(II)=Zn, Mn, Co) and complexes of [Cu₃Cl₆L₄] and CuSO₄L₂·4H₂O, CoSO₄L₂·3H₂O, [ZnSO₄L₃] where L stands for 3-amino-5-methylpyrazole were prepared. The complexes were characterized by elemental analysis, FT-IR spectroscopy, thermal (TG, DTG, DSC and EGA) methods and molar conductivity measurements. Except for the Zn-complexes, the magnetic susceptibilities were also determined. Thermal decomposition of the sulphato complexes of copper(II) and cobalt(II) and the chloro complexes of cobalt(II) and manganese(II) resulted in well-defined intermediates. On the basis of the IR spectra and elemental analysis data of the intermediates a decomposition scheme is proposed. This revised version was published online in August 2006 with corrections to the Cover Date.     

New luminescent heteronuclear Ln(III)–Bi(III) complexes (Ln = Nd,Eu, Tb,Yb) based on aminopolycarboxylic acids

New heteronuclear Ln(III)–Bi(III) complexes (Ln?=?Nd, Eu, Tb, Yb, Lu) with ethylenediamine-N,N,N′,N′-tetraacetic (H₄edta), trans-1,2-cyclohexane-diamine-N,N,N′,N′-tetraacetic (H₄cdta), diethylenetriamine-N,N,N′,N″,N″-pentaacetic (H₅dtpa), and triethylenetetraamine-N,N,N′,N″,N″′,N″′-hexaacetic (H₆ttha) acids have been synthesized with a different synthetic approach. Bi(III) is a sensitizer of the 4f-luminescence in visible and near IR region. Emission spectra of Eu(III)–Bi(III) complexes were studied and the asymmetry of Eu(III) coordination environment was estimated, in good agreement with molecular models. The complexes synthesized by self-assembly are characterized by higher values of the 4f-luminescence quantum yield than other Ln(III)–Bi(III) complexes.     

Synthesis, Spectral Characterization and Electrochemical Properties of New vic-dioxime Complexes Bearing Carboxylate

Three new vic-dioxime ligands, [N-(ethyl-4-amino-1-piperidine carboxylate)-phenylglyoxime (L¹H₂), N-(ethyl-4-amino-1-piperidine carboxylate)-glyoxime (L²H₂), and N,N′-bis(ethyl-4-amino-1-piperidine carboxylate)-glyoxime (L³H₂)], and their Co(II) with Cu(II) metal complexes, were synthesized for the first time. Mononuclear complexes of these ligands with a 1:2 metal-ligand ratio were prepared with Co(II) and Cu(II) salts. The BF₂⁺-capped Co(II) and mononuclear complexes of the vic-dioxime were prepared for [Co(L¹·BF₂)₂] and [Co(L²·BF₂)₂]. The ligands act in a polydentate fashion bonding through nitrogen atoms in the presence of a base, as do most vic-dioximes. The cobalt(II) and copper(II) complexes are non-electrolytes as shown by their molar conductivities (Λ_M) in DMF. The structures of the ligands and complexes were determined by elemental analyses, FT-i.r., u.v.–vis., ¹H- and ¹³C-n.m.r. spectra, magnetic susceptibility measurements, and molar conductivity. The comparative electrochemical studies show that the stabilities of the reduced or oxidized species and the electrode potentials of the complexes are affected by the substituents attached on the oxime moieties of the complexes.     

Redox tuning of mononuclear rhenium(III) complexes containing substituted nitrile andpara-substituted triphenylphosphine ligands

Summary A series of oxorhenium(V) complexes of general formula ReOCl₃[(4-RC₆H₄)₃P]₂ was prepared and converted into rhenium(III) complexes of general formula ReCl₃(MeCN)[(4-RC₆H₄)₃P]₂. Replacement of the coordinated acetonitrile in the complex ReCl₃(MeCN)(Ph₃P)₂ by a series ofpara-substituted benzonitriles yielded complexes of general formula ReCl₃(4-RC₆H₄CN)(Ph₃P)₂. The voltammetric behavior of these oxorhenium(V) and rhenium(III) complexes was characterized. For all three classes of compounds, reversible one-electron oxidations and reductions were observed. The redox potentials were correlated with the pK_a of the substituted phosphine and with the Hammett-Taft constants for both the phosphine and benzonitrile substituent.     

Synthesis, structural and spectral studies of Cu(II) and V(IV) complexes of a novel Schiff base derived from pyridoxal. Antimicrobial activity

A novel Schiff base, N-(4-amino-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one)pyridoxaldimine (HL·HCl), was prepared and structurally characterized on the basis of elemental analyses, ¹H and ¹³C NMR, and IR spectral data. The synthesis and characterization of several Cu(II) (1-6) and V(IV) (7) complexes with N-(4-amino-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one)pyridoxaldimine are reported. The composition and structures of the copper(II) and vanadium(IV) complexes were proposed based on elemental analyses, molar conductance, magnetic susceptibility measurements, IR, electronic and EPR spectroscopy. In addition, the structures of the ligand and the complex [CuL(H₂O)₂]NO₃·2.25H₂O (1) have been determined by single-crystal X-ray diffraction, showing that the Cu(II) center has a distorted square-pyramidal geometry. The ligand and the complexes were also tested for their in vitro antibacterial activity.