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.

In situ study of nanostructure and morphological development during the crystal-mesophase transition of poly(di-n-hexylsilane) and poly(di-n-butylsilane) by X-ray and hot-stage AFM

Nanostructure and morphology and their development of poly(di-n-hexylsilane) (PDHS) and poly(di-n-butylsilane) (PDBS) during the crystal-mesophase transition are investigated using small angle X-ray scattering (SAXS), wide angle X-ray diffraction and hot-stage atomic force microscopy. At room temperature, PDHS consists of stacks of lamellae separated by mesophase layers, which can be well accounted using an ideal two-phase model. During the crystal-mesophase transition, obvious morphological changes are observed due to the marked changes in main chain conformation and intermolecular distances between crystalline phase and mesophase. In contrast to PDHS, the lamellae in PDBS barely show anisotropy in dimensions at room temperature. The nonperiodic structure and rather small electronic density fluctuation in PDBS lead to the much weak SAXS. The nonperiodic structure is preserved during the crystal-mesophase transition because of the similarity of main chain conformation and intermolecular distances between crystalline phase and mesophase.

Study of the interaction between lanthanide ions and a supported bilayer lipid membrane by cyclic voltammetry and ac impedance

The interaction of lanthanide ions with a supported bilayer lipid (1,2-dimyristoyl-sn-glycero-3-phosphatidylcholine) membrane (sBLM) was investigated by cyclic voltammetry and ac impedance spectroscopy in this paper, Lanthanide can affect the conformation of the supported bilayer lipid membrane and cause pore formation. Through the pores, Fe(CN)(6)(3) (4) can reach the electrode surface and show its redox behaviour. Furthermore the redox currents or Fe(CN)(6)(3) (4) increased with increasing concentration of lanthanides and leveled off at 1.2 muM for Eu3+. The interaction ability of three lanthanides with sBLM follows the sequence: Eu3+ > Tb3+ > La3+.

Characterization of organic-inorganic multilayer films by cyclic voltammetry, UV-Vis spectrometry, X-ray photoelectron spectroscopy, small-angle X-ray diffraction and electrochemical impedance spectroscopy

We have employed several techniques, including cyclic voltammetry, UV-Vis spectrometry, small-angle X-ray diffraction, X-ray photoelectron spectroscopy and electrochemical impedance spectroscopy, to characterize the formation processes and interfacial features of ultrathin multilayer films of silicotungstate and a cationic redox polymer on cysteamine-coated Au electrodes self-assembled monolayers. All of these techniques confirm that the multilayer films are built up stepwise as well as uniformly in a layer-by-layer fashion. In particular, the electrochemical impedance spectroscopy is successfully used to monitor the multilayer deposition processes. It has been proved that the electrochemical impedance spectroscopy is a very useful technique in characterization of multilayer films because it provides valuable information about the interfacial impedance features.

Solvent-dependent formation of di- and trinuclear rhodiurn and iridium complexes bridged by N,N '-donor ligands

Reactions of Rh and Ir hydrido complexes. [Rh(H)(2)(PPh3)(2)(solv)(EtOH)]ClO4 (solv = Me2CO, 1a; EtOH, 1b) and [Ir(H)(2)(PPh3)(2)(Me2CO)(2)]BF4 (2), with various N,N'-donor bridging ligands, such as pyrazine (pyz), 4,4'-trimethylenedipyridine (tmdp) and di(4-pyridyl) disulfide (dpds), in some solvents were examined, and their reaction products were characterized by X-ray crystal structure analysis. IR, H-1 NMR and UV-vis spectra. Rh hydrido complexes, la or 1b, formed a dinuclear Rh complex, [Rh-2(PPh3)(2) {(eta(6)-C6H5PPh2}(2)] (ClO4)(2).6CH(2)Cl(2) (3.6CH(2)Cl(2)), in dichloromethane with a reductive elimination of hydrogen. The reactions of 1a or 1b with the pyz ligand in dichloromethane and tetrahydrofuran gave triangular Rh-3 complexes, [Rh-3(PPh3)(6)(pyz)(3)](ClO4)(3).CH2Cl2 (5.CH2Cl2) and [Rh-3(PPh3)(6)(pyz)(3)](ClO4)(3).EtOH (5.EtOH), respectively, in contrast to the formation of a dinuclear Rh hydrido complex, [Rh-2(H)(4)(PPh3)(4)(Me2CO)(2)(pyz)](ClO4)(2).EtOH A-EtOH). in acetone. The reactions of la or 1b with the tmdp ligand in dichloromethane and 3-methyl-2-butanone also afforded dinuclear Rh complexes, [Rh-2(PPh3)(4)(tmdp)(2)](ClO4)(2) (6) and [Rh-2(PPh3)(4)(tmdp)(2)](ClO4)(2).4MeCOCHMe(2) (6.4MeCOCHMe(2)), respectively. On the other hand, Ir hydrido complex 2 reacted with pyz and dpds ligands in dichloromethane to afford dinuclear Ir complexes, [Ir-2(H)(4)(PPh3)(4)(Me2CO)(2)(pyz)]- (BF4)(2).3CH(2)Cl(2) (7.3CH(2)Cl(2)) and [Ir-2(H)(4)(PPh3)(4)(dpds)(2)](BF4)(2).3CH(2)Cl(2).H2O (8.3CH(2)Cl(2).H2O), respectively, without any reductive elimination of hydrogen. Based on structural studies in solution and in the solid state. it was demonstrated that various Rh and Ir complexes were selectively produced depending on the choice of solvents and N,N'-donor bridging ligands.

Study on surface acid-base property of carboxylic acid-terminated self-assembled monolayers by cyclic voltammetry and electrochemical impedance spectroscopy

Cyclic voltammetry and electrochemical impedance spectroscopy were used to study the surface acid-base property of carboxylic acid-terminated self-assembled monolayers (SAMs). A carboxylic acid-terminated thiol, such as thioctic acid (1,2-dithiolane-3-pentanoic add), was self-assembled on gold electrodes. Electron transfer between the bulk solution and the SAM modified electrode was studied at different pH using Fe(CN)(6)(3-) as a probe. The surface pK(a) of thioctic acid was determined by cyclic voltammetry and electrochemical impedance spectroscopy to be 5.6 +/- 0.1 and 5.8 +/- 0.1, respectively. The method is compared with other methods of monolayer pK(a) measurement.

1,1 '-di(tert-butyl)metallocenium cations. The x-ray crystal structures of [M((C5H4Bu)-Bu-t)(2)]PF6 (M = Fe, Co) and [Co((C5H4Bu)-Bu-t)(2)](2)CoCl4

The hexafluorophosphate salts [Fe((C5H4Bu)-Bu-t)(2)]PF6 (1) and [Co((C5H4Bu)-Bu-t)(2)]PF6 (2) crystallize in isotypic structures with centrosymmetric cations which have a staggered (transoid) conformation of the exactly parallel ring Ligands (conformational angle tau = 180 degrees). The tetrachlorocobaltate salt, [CO((C5H4Bu)-Bu-t)(2)](2)CoCl4 (3), contains one almost eclipsed (tau = 140.4 degrees) and one almost staggered (tau = 101.4 degrees) cobaltocenium cation; in both cases, the cyclopentadienyl ring planes are slightly inclined (by alpha = 5.4 degrees and 4.1 degrees, respectively) to give more room to the tert-butyl substituents which are bent away from the metal in all three complexes 1 - 3.

Study of ferric oxide nanoparticles-tris-(2,4-di-t-amylphenoxy)-(8-quinolinolyl) copper phthalocyanine composite LB film

The ferric oxide nanoparticles-tris-(2,4-di-t-amylphenoxy)-(8-quinolinolyl) copper phthalocyanine (CuPcA(2)) composite ultrathin film was obtained by LB (Langmuir-Blodgett) technique. Structure of the composite LB film was characterized by X-ray photoelectron spectra, transmission electron microscopy, infrared spectra and visible spectra. Gas sensitivity measurements indicate that the composite LB film is sensitive to 100-200 ppm C2H5OH at room temperature. (C) 2000 Elsevier Science S.A. All rights reserved.

Investigation of the electrocatalytic effect of polyaniline on the redox reaction of 2,5-dimercapto-1,3,4-thiadiazole by cyclic voltammetry

Electrochemical polymerized polyaniline(PAn) film electrode was used to investigate the electrocatalytic effect of PAn on the electrochemical redox reaction of 2,5-dimercapto-1,3,4-thiadiazole (DMcT), PAn film electrode was electrochemically treated or immersed in DMcT solution before it was scanned in 1.0 mol/L HCl electrolyte. The cyclic voltammograms of PAn film electrode in 1.0 mol/L HCl solution changed with the above treatment, implying the electrocatalytic effect of PAn on the redox reaction of DMcT, The formation of electron-donor-acceptor adducts through the interaction between thiol or disulfide groups of DMcT and amine or imine groups of PAn during the treatment was probably the reason of the catalysis, The electrochemical properties of the adduct were different from those of PAn and DMcT, The adduct possessed a higher electrochemical activity and a better electrochemical reversibility than DMcT or PAn used alone.

Hydrothermal synthesis and structure of [{Mo8V4O36(VO4)(VO)(2)}(n)](7n-) bi-capped alpha-Keggin fragments linked to a chain

The title compound, (H(2)en)(3)H3O {MO8V4O36 (VO4) (VO)(2)} . 4H(2)O, was hydrothermally synthesized and structurally characterized by means of IR, ESR spectrum and single crystal X-ray diffraction. It crystallized in a monoclinic system with space group P2(1)/c, a=1. 980 4(4) nm, b=2. 063 4(4) nm, c=1. 192 0(2) nm, (beta =94. 76(3)degrees and deep black colour. The compound contains V-centered bi-capped alpha -Keggin fragments {Mo8V7O42} that are linked together by edge-shared units (VO5)-O-N via V-O-V bonds, forming a chain.

Analysis of poly (arylene phosphonate) cyclic oligomer by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MAIDI-TOF-MS) was used for analysis of poly(arylene phosphonate) cyclic oligomers. A comparison was made by using 1,8,9-dithranol, 2,5-dihydroxybenzoic acid and retinoic acid as the matrix. The result showed that the retinoic acid produced the strongest ion signals under the conditions used. Different salts of metals were used as the cationization agents to examine the effect on the cyclic oligomers. It was found that the salts could produce metal-cyclic oligomer cation spectra and lithium was the stronger one than those of silver so, the suitable matrix and cationization agent for the new cyclic oligmer were obtained. They were very effective for the analysis of poly(arylene phosphonate) cyclic oligomer.

Investigation of proton transfer across the water/1,2-dichloroethane interface by o-phenanthroline using glass micro/nano-pipets and cyclic voltammetry

Facilitated proton transfer across the water/1,2-dichloroethane (DCE) interface supported on the tips of micro- and nano-pipets by o-phenanthroline (Phen) was studied by using cyclic voltammetry. The formed micro- and nano-liquid/liquid interfaces functioned as micro- and nano-electrodes under certain experimental conditions. The dependence of the half-wave potentials on the aqueous solutions acidities was studied and the ratio of association constants between Phen and proton in the aqueous and DCE phases was calculated by the method proposed by Matsuda et al.. The standard rate constant (k(0)) and the transfer coefficient (alpha) evaluated by using nano-pipets were equal to 0.183 +/- 0.054 cm/s and 0.70 +/- 0.09, respectively.

Syntheses and crystal structures of novel di- and trinuclear rhodium complexes bridged by pyrazine

Never di- and trinuclear Rh complexes, [Rh-2(PPh3)(4)(H)(4)(Me2CO)(2)(mu -pyz)](ClO4)(2). EtOH and [Rh-3(PPh3),(mu -pyz)(3)](ClO4)(3). EtOH were selectively isolated from the reaction of [Rh(PPh3)(2)(H)(2)(Me2Co)(EtOH)]ClO4 with pyrazine (pyz) in Me2CO and THF, respectively. Their structures were crystallographically characterized.

Characterization of cyclic arylether ketone (sulfone) containing hexafluoroisopropylidene unit by matrix-assisted laser desorption ionization time-of-flight mass spectrometry

The cyclic aryletherketone( sulfone) oligomers containing hexafluoroisopropylidene unit were characterized by matrix-assisted laser desorption ionization time-of-night mass spectrometry(MALDI-TOF-MS) using Na+ and Ag+ as cationization agents. The affinities of cyclic oligomers to the cation were studied. The analysis result showed that 1,8,9-dithranol, in the presence of silver trifluoroacetate, was very effective for the characterization of cyclic arylether ketone ( sulfone) containing hexafluoroisopropylidene unit.

Cyclic voltammetric and in situ Fourier transform infrared spectroelectrochemical studies on the reaction of Cd2+ on the plussian blue/platinum modified electrode

Plussian blue(PB)/Pt modified electrode Tvas studied in the CdCl2 electrolyte solution by cyclic voltammetry and in situ FTIR spectroelectrochemistry. It was found that Cadmium ion was capable of substituting the high-spin iron of PB in an electrochemically induced substitution reaction and hexacyanoferrate cadmium (CdHCF) can be formed in the PB film. But PB and CdHCF in mixture film showed their own electrochemistry properties without serious effect on each other. The mechanism of substitution reaction has been given in detail.