Structural modelling of Eu3+-based siloxane-poly( oxyethylene) nanohybrids

The modelling of the local structure of sol-gel derived Eu3+-based organic/inorganic hybrids is reported, based on Small-Angle X-ray Scattering (SAXS), photoluminescence and mid-infrared spectroscopy. The hybrid matrix of these organically modified silicates, classed as di-ureasils and termed U(2000) and U(600), is formed by poly( oxyethylene) (POE) chains of variable length grafted to siloxane domains by means of urea cross-linkages. Europium triflate, Eu(CF3SO3)(3), was incorporated in the two di-ureasil matrices with compositions 400 greater than or equal ton greater than or equal to 10, n is the molar ratio of ether oxygens per Eu3+. The SAXS data for undoped hybrids (n=infinity) show the presence of a well-defined peak attributed to the existence of a liquid-like spatial correlation of siloxane rich domains embedded in the polymer matrix and located at the ends of the organic segments. The obtained siloxane particle gyration radius Rg(1) is around 5 Angstrom (error within 10%), whereas the interparticle distance d is 25 +/-2 Angstrom and 40 +/-2 Angstrom, for U(600) and U(2000), respectively. For the Eu3+-based nanocomposites the formation of a two-level hierarchical local structure is discerned. The primary level is constituted by strongly spatially correlated siloxane particles of gyration radius Rg(1) (4-6 and 3-8 Angstrom, errors within 5%, for U(600())n Eu(CF3SO3)(3), 200 greater than or equal ton greater than or equal to 40, and U(2000)(n)Eu(CF3SO3)(3), 400 greater than or equal ton greater than or equal to 40, respectively) forming large clusters of gyration radius Rg(2) (approximate to 75 +/- 10 Angstrom). The local coordination of Eu3+ in both di-ureasil series is described combining the SAXS, photoluminescence and mid-infrared results. In the di-ureasils containing long polymer chains, U(2000)(n)Eu(CF3SO3)(3), the cations interact exclusively with the carbonyl oxygens atoms of the urea bridges at the siloxane-POE interface. In the hybrids containing shorter chains, U(600)(n)Eu(CF3SO3)(3) with n ranging from 200 to 60, the Eu3+ ions interact solely with the ether-type oxygens of the polymer chains. Nevertheless, in this latter family of hybrids a distinct Eu3+ local site environment involving the urea cross-linkages is detected when the europium content is increased up to n=40.

Synthesis, characterization and initial biological studies of a new platinum(II) complex with deoxyalliin

A new platinum(II) complex with deoxyalliin was synthesized and characterized by chemical and spectroscopic techniques. Elemental and mass spectrometry analyses of the solid complex fit to the composition [Pt(C6H11NO2S)Cl-2] center dot H2O. C-13 NMR, N-15 NMR and infrared spectra of the complex are consistent with coordination of deoxyalliin to Pt( II) through the nitrogen and sulfur atoms forming a square-planar geometry. The complex is soluble in dimethylsulfoxide. Biological analysis for evaluation of a potential cytotoxic effect of the complex was performed using HeLa cells, a human cervix adenocarcinoma-derived cell line. The results were compared with those of a palladium( II) complex previously described.

Characterization and catalytic activity of 2,6-dichlorophenyl substituted iron(III) porphyrin supported on silica gel and imidazole propyl gel

In this work we have made use of the study of the interaction between Fe(TDCPP)(+) and the axial ligands OH- and imidazole in order to help characterize the heterogenized catalysts Fe(TDCPP)SG and Fe(TDCPP)IPG through UV-VIS and EPR spectroscopies and thus, better understand their different catalytic activity in the oxidation of cyclohexane by PhIO. We have found out that in Fe(TDCPP)SG (containing 1.2 X 10(-6) mol Fe(TDCPP)(+)/g of support), the FeP bis-coordinates to silica gel through Fe-O coordination and it is high-spin (FeP)-P-III species. In Fe(TDCPP)IPG 1 (containing 1.1 X 10(-6) mol Fe(TDCPP)(+) and 2.2 X 10(-4) mol imidazole/g of support), the FeP is bis-ligated to imidazole propyl gel through Fe-imidazole coordination and using NO as a paramagnetic probe, we present evidence that Fe(TDCPP)(+) is present as a mixture of low-spin (FeP)-P-III and (FeP)-P-II species. This catalyst led to a relative low yield of cyclohexanol (25%) because the bis-coordination of the (FeP)-P-III to the support partially blocks the reaction between Fe(TDCPP)(+) and PhIO, thus leading to the formation of only a small amount of the active species Fe-IV(OP+, while the (FeP)-P-II species do not react with the oxygen donor. Increasing the amount of Fe(TDCPP)(+) and decreasing the amount of imidazole in the support led to the obtention of high-spin (FeP)-P-III EPR signals in the spectra of Fe(TDCPP)IPG 5 (containing 4.4 X 10(-6) mol Fe(TDCPP)(+) and 2.2 X 10(-5) mol imidazole/g of IPG), together with low-spin (FeP)-P-III species. This latter catalyst led to better cyclohexanol yields (67%) than Fe(TDCPP)IPG 1. Fe(TDCPP)IPG 5 was further used in a study of the optimization of its catalytic activity and in recycling experiments in the optimized conditions. Recycling oxidation reactions of Fe(TDCPP)IPG 5 led to a total turnover number of 201 and total cyclohexanol yield of 201%, which could not be attained with Fe(TDCPP)Cl in homogeneous solution (turnover = 96) due to the difficulty in recovering and reusing it.

H-1-N-15 NMR studies of the complex bis(S-allyl-L-cysteinate)palladium(II)

H-1-N-15 2D NMR data for S-allyl-L-cysteine (deoxyalliin) and for bis(S-allyl-L-cysteinate)palladium(II) complex are presented in this manuscript. Large upfield N-15 NMR shift of the amine nitrogen in the spectrum of the complex when compared to the spectrum of the ligand shows clearly coordination of S-allyl-L-cysteine, in the anion form, to palladium(II) through the NH2 group. (c) 2005 Elsevier B.V. All rights reserved.

Synthesis, spectroscopic characterization and molecular modeling of a tetranuclear platinum(II) complex with thiazolidine-4-carboxylic acid

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Chemical, spectroscopic characterization, and in vitro antibacterial studies of a new gold(I) complex with N-acetyl-L-cysteine

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Synthesis, thermal properties and spectroscopic study of solid mandelate of light trivalent lanthanides

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Synthesis and characterization of a platinum(II) complex with N-acetyl-L-cysteine

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Chemical and spectroscopic studies of a new palladium(II) complex with N-acetyl-L-cysteine

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Synthesis of a functionalized europium complex and deposition of luminescent Langmuir-Blodgett (LB) films

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Characterization and biological studies of a new platinum(II) complex with the amino acid L-alliin

Synthesis and characterization of a new Pt(II) complex with the amino acid L-alliin (S-allyl-L-cysteine sulfoxide, C(6)H(11)NO(3)S) are described. Elemental and mass spectrometric analyses of the solid complex are consistent with [PtCl(2)(alliin)], or [PtCl(2)(C(6)H(11)NO(3)S)]. (13)C nuclear magnetic resonance (NMR), [(1)H-(15)N] two dimensional (2D) NMR and infrared spectroscopy indicate coordination of the ligand to Pt(II) through the N and S atoms. The complex is very soluble in dimethyl sulfoxide. Biological analysis for evaluation of a potential cytotoxic effect of the complex was performed using HeLa cells derived from human cervical adenocarcinoma. The complex presented moderate cytotoxic activity, inducing about 40% cell death at a concentration of 400 mol L(-1).

Synthesis and solid-state structural characterization of bis (thiocyanatemercury)tetracarbonyliron

The bis (thiocyanatemercury)tetracarbonyliron, [Fe(CO)4(HgSCN)2], was prepared from [Fe(CO) 5] and Hg(SCN)2, and studied by IR spectroscopy and X-ray diffraction. The compound crystallizes in the tetragonal space group I4,1/a. The unit cell, with dimensions of a = 13.778(3), c = 13.234(3) Å, V = 2512.3(9) Å3, contains four molecules. The iron atom is octahedrally coordinated by four carbonyl groups and two mercury atoms in cis positions. The coordination of the mercury atoms is distorted square-planar, since, besides mercury-iron and mercury-sulphur bonds, there are also mercury-mercury and mercury-nitrogen interactions. The FeHg distance is 2.506(5)Å and the HgFeHg angle is 78.0(1)°. © 1987.

Kinetics, electrochemistry and resonance raman spectra of the (2-mercaptopyridine) (edta)ruthenium(III) complex

The chemistry of the pentadentate edta complexes of ruthenium(III) and (II) with 2-mercaptopyridine (HSpy) has been investigated based on spectroscopic, kinetic and electrochemical techniques. The reaction of [Ru(III)(edta)H2O]- with HSpy proceeds with a specific rate of 1.05 × 104 M-1 S -1 (25°C, I = 0.10 M, acetate buffer), forming a red complex (λmax = 550 nm) which undergoes a relaxation process as a function of pH, with an apparent pKa = 4.35 and kobs = 0.31 S -1. The second reaction depends on the concentration of HSpy and leads to a stable green product (λmax = 630 mn). A pronounced enhancement has been observed in the Raman spectra of the complexes, particularly in the region of the metal-ligand vibrations. The electronic and resonance Raman spectra are consistent with the coordination of HSpy via the sulfur atom in the red complex, and with a chelate binding in the green species. © 1987.

Preparation, characterization and spectroscopy of the europium diphenylphosphinate complex

The purpose of this work is to study the preparation and spectroscopic behavior of the europium diphenylphosphinate complex -Eu(DPP)3. Elemental and thermogravimetric analysis, powder X-ray diffractometry, and infrared spectroscopy were applied to characterize the formula of the final product and the sixfold coordination of the Eu3+ ion. Excitation and emission spectra have been recorded at liquid nitrogen and room temperatures. The 5D0→7F2 transition intensity decreases when T decreases in comparison to the 5D0→7F1 transition intensity. Molecular mechanic calculations were developed in order to obtain the spatial coordinates of the Eu3+ and ligand ions. The simple overlap model was used to calculate the total splitting of the 5D0→7F1 transition, 5D0→7F0/5D 0→7F2 ntensity ratio and the intensity parameters, Ωλ (λ=2 and 4). Good agreements between theoretical predictions and experimental results have been obtained with g=2/3 as the effective charge and α=0.8×10-24 cm3 as the isotropic polarizability of the oxygen. © 1998 Elsevier Science S.A.

White light emission of Eu3+-based hybrid xerogels

The luminescence spectra and extended x-ray-absorption fine-structure (EXAFS) measurements of a series of Eu3+-based organic/inorganic xerogels were reported and related to the local coordination of the lanthanide cations. The hybrid matrix of these organically modified silicates, classed as U(2000) ureasils, is a siliceous network to which short organic chains containing oxyethylene units are covalently grafted by means of urea bridges. The luminescent centers were incorporated as europium triflate, Eu(CF3SO3)3, and europium bromide, EuBr3, with concentrations 200≥n≥20 and n=80, 40, and 30, respectively - where n is the number of ether oxygens in the polymer chains per Eu3+ cation. EXAFS measurements were carried out in some of the U(2000)nEu(CF3SO3)3 xerogels (n=200, 80, 60, and 40). The obtained coordination numbers N ranging from 12.8, n=200, to 9.7, n=40, whereas the average Eu3+ first neighbors distance R is 2.48-2.49 Å. The emission spectra of these multiwavelength phosphors superpose a broad green-blue band to a series of yellow-red narrow 5D0→7F0-4 Eu3+ lines and to the eye the hybrids appeared to be white, even at room temperature. The ability to tune the emission of the xerogels to colors across the chromaticity diagram is achieved by changing the excitation wavelength and the amount of salt incorporated in the hybrid host. The local environment of Eu3+ is described as a continuous distribution of closely similar low-symmetry network sites. The cations are coordinated by the carbonyl groups of the urea moieties, water molecules, and, for U(2000)nEu(CF3SO3)3, by the SO3 end groups of the triflate anions. No spectral evidences have been found for the coordination by the ether oxygens of the polyether chains. A mean radius for the first coordination shell of Eu3+ is calculated on the basis of the emission energy assignments. The results obtained for U(2000)nEu(CF3SO3)3, 2.4 Å for 90 ≥n≥40 and 2.6 and 2.5 Å for n=30 and 20, respectively, are in good agreement with the values calculated from EXAFS measurements. The energy of the intraconfigurational charge-transfer transitions, the redshift of the 5D0→7F0 line, with respect to the value calculated for gaseous Eu3+, and the hypersensitive ratio between the 5D0→7F2 and 5D0→7F1 transitions, point out a rather low covalency nature of the Eu3+ first coordination shell in these xerogels, comparing to the case of analogous polymer electrolytes modified by europium bromide. ©1999 The American Physical Society.