Synthesis and characterization of novel lanthanocene complexes with dichalcogenolate o-carboranyl ligands

Reactions of [ Cp(2)Ln(mu-Cl)](2) (Cp = eta(5)-C5H5, Ln = Nd, Yb, Dy, Gd, Er) with an equivalent of [ (THF)(3)LiE2C2B10H10Li. (TT-IF) (THF)](2) (E = S, Se) in THF afforded the dinuclear sandwich complexes of formula[Cp(2)LnE(2)C(2)B(10)H(10)](2)[Li(THF)(4)](2) [E = S, Ln = Nd (1a), Yb (2a), Dy (3a), Gd (4a), Er (5a); E = Se, Ln = Nd (1b), Yb (2b), Dy (3b), Gd (4b), Er (5b)]. The molecular structures of complexes la, 2a and 2b were determined by the single crystal X-ray structure analyses. Two lanthanide atoms are connected by a pair chalcogen (eta(1), eta(2)-E2C2B10H10) bridging ligands and the central Ln(2)E(2) four membered ring is not planar.

Sol-gel derived iridium composite glucose biosensor

Iridium powder is introduced into sol-gel process for the first time to fabricate a novel type of sol-gel derived metal composite electrode. The iridium ceramic electrode shows excellent electrocatalytic action for both oxidation and reduction of hydrogen peroxide. The glucose biosensor based on sol-gel derived iridium composite electrode was fabricated. The biosensor shows highly selectivity towards glucose because of the strong catalytic action of iridium composite matrix for enzyme-liberated hydrogen peroxide at low operating potential, at which common interferences cannot be sensed. The novel type of biosensor can be renewed by simply mechanical polishing with favorable reproducibility and long-term stability.

Hybrid organic-inorganic compounds doped with terbium carboxyl complexes produced in situ via a sol-gel approach

In situ synthesis of terbium carboxyl complexes in an organic-inorganic hybrid matrix by a sol-gel process has been proposed. The formation of terbium carboxyl complexes in the hybrid matrix is confirmed by the luminescence spectra and IR spectra. It is observed that the location at the amino group in aminobenzoic acid has a large effect on the luminescence properties and lifetimes. Furthermore, the emission intensity decreases with increasing temperature.

Luminescence properties of lanthanide complexes doped in hybrid material from tetraethoxysilane and 3-glycidyioxyropyl-trimethoxysilane

Hybrid materials, containing in-situ synthesized lanthanide complexes with intense green light, have been prepared via sol-gel process. The luminescence properties and the decay times of as-synthesized samples were investigated. The excitation spectrum of the samples indicates the formation of complexes between terbium (III) and P-Sulfosalicylic acid. The hybrid materials that contain in-situ synthesized terbium complexes exhibit the characteristic emission bands of the rare earth ions. In addition, the effect of concentration of terbium on the luminescence properties as well as the thermal stability were also studied.

Luminescence properties of transparent hybrid thin film covalently linked with lanthanide complexes

Novel hybrid thin films covalently doped with Eu3+ (Tb3+) have been prepared via direct routes involving co-condensation of tetraethoxysilane and phen-Si in the presence of Eu3+ (Tb3+) by spin-casting and their luminescence properties have been investigated in detail. Lanthanide ions can be sensitized by anchored phenanthroline in hybrid thin films. Excitation at the ligand absorption wavelength (272 nm) resulted in the strong emission of the lanthanide ions i.e. Eu3+ D-5(0)-F-7(J) (J=0, 1, 2, 3, 4) emission lines and Tb3+ D-5(4)-F-7(J) (J = 6, 5, 4, 3) due to the energy transfer from the ligands to the lanthanide ions.

Study on highly ordered luminescent Langmuir-Blodgett films of heteropolytung state complexes containing lanthanide

Luminescent thin films of heteropolytungstate complexes containing lanthanide (europium or samarium) were successfully fabricated by the Langmuir-Blodgett (LB) technique. The pressure-area isotherm of the monolayer of dimethyldioctadecylammonium. bromide (DODA) is modified rather markedly when the subphase contains the complex of Na9EuW10O36 or Na9SmW10O36. The above results indicate that the monolayer of DODA has a strong interaction with the polyanions of EuW10O369-. (or SmW10O369-). X-ray photoelectron spectra and fluorescent spectra verify that europium and tungsten atoms are 36 36 incorporated into the LB films. Ultraviolet (UV), fluorescent spectra and low-angle X-ray diffraction experiments demonstrate that these LB films have a well-defined lamellar structure. The LB film containing EuW10O369- can give off strong fluorescence 16 on UV irradiation. The characteristic emission behaviors of europium ions in LB films and in the powder of Na9EuW10O369- are discussed. It is found that the intensity ratio of the D-5(0)-F-7(2) transition to the D-5(0)-->F-7(1) transition in LB film is quite different from that in the powder of Na9EuW10O36. The difference of the ratio indicates that the site symmetry of europiurn is distorted in LB film, which is probably due to the strong electrostatic interactions between DODA and polyanions.

Preparation and luminescence properties of hybrid materials containing europium(III) complexes covalently bonded to a silica matrix

A new kind of luminescent organic-inorganic hybrid material (denoted Hybrid I) consisting of europium 1,10-phenanthroline complexes covalently attached to a silica-based network was prepared by a sol-gel process. 1,10-Phenanthroline grafted to 3-(triethoxysilyl)propyl isocyanate was used as one of the precursors for the preparation of an organic-inorganic hybrid materials. For comparison purposes, the hybrid material (denoted Hybrid II) in which phenanthroline was not grafted onto the silica backbone of the frameworks was also prepared. Elemental analysis; NMR, FT-IR, UV/vis absorption, and luminescence spectroscopies, and luminescence decay analysis were used to characterize the obtained hybrid materials. It is shown that the homogeneity of Hybrid I is superior to that of Hybrid II, and a higher concentration europium can be incorporated into Hybrid I than Hybrid II. Excitation at the ligand absorption wavelength (283 nm) resulted in the strong emission of the Eu3+ D-5(0)-F-7(J) (J = 0-4) transition lines as a result of the efficient energy transfer from the ligands to the EU3+ in Hybrid I. The number of water molecules coordinated to the europium ion was estimated, and the structure of the as-synthesized Hybrid I was predicted on the basis of the experimental results.

Dinuclear half-sandwich complexes containing bridging 1,2-dicarba-closo-dodecaborane-1,2-dichalcogenolato ligands. Molecular structures of Cp2Fe2(CO)(3)[mu-Se2C2(B10H10)], Cp2Ru2[mu-S2C2(B10H10)](2), and CP*Ru-2(2)(mu-Se)[mu-Se2C2(B10H10)].

Three prototypes of dinuclear complexes were obtained from the reactions of dilithium 1,2-dicarbacloso-dodecaborane-1,2-dichalcogenolates, (B10H10)C-2-(ELi)(2) (E = S, Se), with CpFe(CO)(2)Cl (1), CpRu(PPh3)(2)Cl (2), or [Cp*RuCl2](2) (3), respectively, and their structures have been determined by X-ray crystallography.

Self-immobilized catalysts for ethylene polymerization: neutral, single-component salicylaldiminato phenyl nickel(II) complexes bearing allyl substituents

A new family of self-immobilized ethylene polymerization catalysts, derived from neutral, single-component salicylaldiminato phenyl nickel complexes, is described.

Synthesis and characterization of tris(cyclopentylcyclopentadienyl)lanthanide complexes (C5H9C5H4)(3)NdBrLi(THF)(3) and (C5H9C5H4)(3)SmTHF

(C5H9C5H4)(3)NdBrLi(THF)(4)(1)(C5H9=cyclopentyl) was obtained from the reaction of NdCl3 with C5H9C5H4Na and LiBr (Nd:Na:Li=1:2:1 molar ratio) in THE X-ray crystallography showed that the ten-coordinated neodymium atom is bonded to three cyclopentylcyclopentadienyl(eta(5)) rings and a single bromine atom bridging a lithium which is bonded to three THF molecules. Complex 1 is triclinic, P1 space group with unit dimensions of a= 12.048(2), b= 13.498(3), c= 13.831(3)Angstrom, a = 104.16(3), beta = 104.07(3), gamma =95.96(3)degrees, V=2083.3(7)Angstrom(3), Z=2, D-c=1.35Mg/m(3) and F(000)=874. (C5H9C5H4)(3)SmTHF (2) was synthesized by reaction of anhydrous SmCl3 with C5H9C5H4Na at a molar ratio of 1:3. The structure was determined by X-ray crystallography. The ten-coordinated samarium atom is bonded to three cycloperrtylcyclopentadienyl rings and one oxygen of THF molecule to form a pseudo-tetrahedron. Complex 2 is orthorhombic, Fdd2 space group with unit cell dimensions of a =28.175(5)Angstrom, b =46.24(2) Angstrom, c =9.167(4) Angstrom(3), V=11943(8)Angstrom(3), Z= 16, D-c = 1.38Mg/m(3) and F(000)=5136.

Sol-gel preparation and luminescence properties of nano-structured hybrid materials incorporated with europium complexes

Microporous silica gel has been prepared by the sol-gel method utilizing the hydrolysis and polycondensation of tetraethylorthosilicate (TEOS). The gel has been doped with the luminescent ternary europium complex Eu(TTA)(3)(.)phen: where HTTA=1-(2-thenoyl)-3,3,3-trifluoracetone and phen=1,10-phenanthroline. By contrast to the weak f-f electron absorption bands of Eu3+, the complex organic ligand exhibits intense near ultraviolet absorption. Energy transfer from the ligand to Eu3+ enables the production of efficient, sharp visible luminescence from this material. Utilizing the polymerization of methyl methacrylate, the inorganic/polymer hybrid material containing Eu(TTA)(3)(.)phen has also been obtained. SEM micrographs show uniformly dispersed particles in the nanometre range. The characteristic luminescence spectral features of europium ions are present in the emission spectra of the hybrid material doped with Eu(TTA)(3)(.)phen.

Synthesis and electrochemical characteristics of lanthanide complexes with 2-nitro-5,10,15,20-tetraphenylporphyrin and acetylacetonate

Four lanthanide complexes with 2-nitro-5,10,15,20-tetraphenylporphyrin and acetylacetonate were prepared and characterized by elemental analyses, LR, UV-Visible,H-1 NMR, XPS and molar conductance. The redox properties of the lutetium complex with 2-nitro-5,10,15,20-tetraphenylporphyrin and acetylacetonate in dichloromethane were studied by cyclic voltammetry.

Preparation, characterization and photophysical properties of layered zirconium bis(monohydrogenphosphate) intercalated with rare earth complexes

Two kinds of rare earth (RE) complexes were intercalated into zirconium bis(monohydrogenphosphate) (alpha -ZrP) by exchanging the RE complexes into the p-methyoxyaniline (PMA) preintercalated compound Zr(O3POH)(2). 2PMA (alpha -ZrP . 2PMA). Powder X-ray diffraction patterns reveal that Eu(DBM)(3)phen (DBM: dibenzoylmethane, phen: 1,10-phenanthroline) and Tb(AA)(3)phen (AA: acetylacetone) intercalated into alpha -ZrP . 2PMA. This was confirmed by the UV-visible spectra of both the RE complexes and the assemblies. At the same time, the assemblies have better luminescent properties, and the fluorescent lifetimes of RE3+ in the excited state in the assemblies are much longer than those in the complexes. The stabilities of the assemblies under UV radiation are much better than those of the RE complexes.

Preparation and luminescence properties of sol-gel hybrid materials incorporated with europium complexes

Microporous silica gel has been prepared by the sol-gel method utilizing the hydrolysis and polycondensation of tetraethylorthosilicate (TEOS). The gel has been doped with the luminescent ternary europium complex Eu(TTA)(3). phen: where HTTA = 1-(2-thenoyl)-3,3,3-trifluoracetone and phen = 1,10-phenanthroline. By contrast to the weak f-f electron absorption bands of Eu3+, the complex organic ligand exhibits intense near ultraviolet absorption. Energy transfer from the ligand to Eu3+ enables the production of efficient, sharp visible luminescence from this material. Utilizing the polymerization of methyl methacrylate or ethyl methacrylate, the inorganic/polymer hybrid materials containing Eu(TTA)(3). phen have also been obtained. SEM micrographs show uniformly dispersed particles in the nanometre range. The characteristic luminescence spectral features of europium ions are present in the emission spectra of the hybrid material doped with Eu(TTA)3 phen. (C) 2000 Kluwer Academic Publishers.