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.

Synthesis, properties and X-ray crystal structure of a new heteropolyacid supermolecular charge-transfer complex [(VB1)(2)DMFHPMo12O40 center dot 5DMF]

The title complex [(VB1)(2)DMFHPMo12O40.5DMF, VB1 = vitamin B-1 (thiamine chloride), DMF = N,N-dimethylformamide] has been synthesized and characterized by elemental analysis, IR, UV-Vis, electron spin resonance, X-ray photoelectron spectroscopy and cyclic voltammetry methods. The X-ray crystal structure revealed that there is one independent molecule in the unit cell of the title complex that contains one mixed-valence heteropolyanion, two VB1+ cations and six DMF molecules. The title complex possesses a centrosymmetrical arrangement in the unit cell, with the P atom at the symmetry center of the heteropolyanion and with eight O atoms surrounding the central P atom, such that two sets of PO4 tetrahedra are formed. The PO4 tetrahedra and MoO66-(7-) octahedra are disordered in the heteropolyanion. The bond distances of P-O-a and Mo=O-d are in the ranges 1.57 (4)-1.70 (4) Angstrom and 1.61 (2)-1.67 (2) Angstrom, respectively.

Syntheses and crystal structures of mononuclear rhodium hydrido complexes from the reactions of [Rh(H)(2)(PPh3)(2)(EtOH)(2)]ClO4 with various nitrogen ligands

Reactions of the Rh hydrido complex [Rh(H)(2)(PPh3)(2)(EtOH)(2)]ClO4 (1) With nitrogen ligands such as 2-(4-thiazolyl)benzimidazole (tbz). pyridazine (pdz), imidazole (im) and pyrimidine (pmd) in CH,Cl, afforded Various mononuclear Rh hydrido complexes, [Rh(H)(2)(PPh3)(2)(tbz)]CIO4 (2), [Rh(H)(2)(PPh3)(2)(pdZ)(2)]ClO(4)(.)2CH(2)Cl(2) (3). [Rh(H)Cl(PPh3)(2)(pdz)(2)](ClO4CH2Cl2)-C-. (4). [Rh(H)(2)(PPh3)(2)(im)(2)]ClO(4)(.)2CH(2)Cl(2) (5). [Rh(H)Cl(PPh3)(2)(im)(2)](ClO4CH2Cl2)-C-. (6). [Rh(H)(2)(PPh3)(2)(pmd)(2)](ClO4CH2Cl2)-C-. (7) and the Rh non-hydrido complex [RhCl2(pmd)(4)]ClO4 (8). The Rh complexes 2. 3, 5 and 6 were crystallographically characterized. The formation process was monitored by H-1 NMR and UV-Vis spectra. In all the Rh hydrido complexes, the Rh atom is coordinated by two PPh3. ligands in trans-positions and two nitrogen ligands in the cis-positions. The remaining sites Lire occupied by one or two hydride atoms to form a saturated 18-electron framework in a slightly distorted octahedral geometry. For complex 2 an appreciable inter-molecular pi interaction is observed between planes of tbz and PPh3 ligands, while an intra-molecular hydrogen bonding interaction between C-H and Cl atoms is found in complex 6.

Hydrothermal synthesis and crystal structure of a hybrid material based on [Co-4(phen)(8)(H2O)(2)(HPO3)(2)](4+) and a highly reduced polyoxoanion

An unusual composite hybrid material [Co-4 (phen)(8) (H2O)(2) (HPO3)(2)](H3O)(3) [PMo8VI V-4(IV) O-40 ((VO)-O-IV) 2] 1 (phen = 1,10-phenanthroline) has been hydrothermally synthesized from a mixture of NH4VO3, Na2MoO4.2H(2)O, CoCl2.6H(2)O, phen, H3PO3 and water. It was characterized by elemental analysis, IR, UV-vis, XPS, EPR, TG and single crystal X-ray diffraction. The title compound is constructed from the organic-inorganic hybrid [Co-4(phen)(8)(H2O)(2) (HPO3)(2)](4+) and highly reduced bi-capped pseudo-Keggin [(PMo8V4O40)-V-VI-O-IV ((VO)-O-IV)(2)](7-) polyoxoanions The structure exhibits an extended 2D network through hydrogen bonds among cations, anions and H2O, combining polyoxometalates with metal phosphonates for the first time.

A highly reduced polyoxoanion with phosphorus-centered alternate layers of Mo/V oxides, [(PMo2Mo6V4O40)-Mo-V-V-VI-O-IV((VO)-O-IV)(2)](9-)

An unusual polyoxometalate [H2N(C2H4)(2)NH2](4)(H3O)[(PMO2Mo6V4O40)-Mo-V-V-VI-O-IV((VO)-O-IV)(2)].H2O is hydrothermally synthesized and characterized by IR, UV-VIS, elemental analyses, X-ray photoelectron spectrum, ESR, TG and Single crystal X-ray diffraction. The title compound crystallizes in the orthorhombic space group Pbca with a = 15-227(5), b = 19.491(4), c = 18.737(3) Angstrom, V = 5123(2) Angstrom(3), Z = 4, and R-1 (wR(2)) = 0.0726(0.1416). The compound contains an unusual highly reduced pseudo-Keggin type polyoxoanion and exhibits an interesting phosphorus-centered alternate arrangement of layers of molybdenum and vanadium oxides.

Preparation and nonlinear optical properties of ultrathin composite films containing both a polyoxometalate anion and a binuclear phthalocyanine

An ultrathin composite film containing both polyoxometalate anion [PMo12O40](3-) ( PMo12) and a planar binuclear phthalocyanine, bi-CoPc, has been prepared by the electrostatic layer-by-layer self-assembly method. UV-vis measurements revealed regular film growth with each four-layer {PMo12/bi-CoPc/PSS/PAH} adsorption. The lm structure was characterized by small-angle X-ray reflectivity measurements, X-ray photoelectron spectra, and AFM images. The nanothick film shows a third-order nonlinear optical response of chi((3)) = 4.21 x 10(-12) esu. Experimental investigations also indicate that the combination of polyoxometalate anions [PMo12O40](3-) with the phthalocyanine bi-CoPc in multilayer films can enhance the third-order NLO susceptibility and modify the third-order NLO absorption of bi-CoPc.

Preparation, characterization and luminescence properties of ultrathin films containing polyoxometalates

Ultrathin multilayer films of poly(allylamine hydrochloride) (PAH) and a polyoxotungstoeuropate cluster K-13[Eu(SiW11O39)(2)] (Eu(SiW11)(2)) have been prepared by the layer-by-layer self-assembly method. The Eu(SiW11)(2)/PAH multilayer films have been characterized by X-ray photoelectron spectra and atomic force microscopy (AFM). UV-Vis measurements reveal regular film growth with each Eu(SiW11)(2) adsorption. The photoluminescent behavior of the film at room temperature was to show the characteristic Eu3+ emission pattern of D-5(o) --> F-7(J). The occurrence of photoluminescent activity confirms the potential for creating luminescent multilayers with polyoxometalates.

Studied on the interactions of antibody-porphyrin by circular dichroism and ultraviolet-visible spectrophotometry

Circular dichoism and UV-vis measurements were used to study the interaction between porphyrin and monoclonal antibodies ( McAbs). McAbs-porphyrin complex formation is usually accompanied by significant bathochromic shift and hyperchromicity changes of the absorption maxima in the porphyrin soret band region. Induced CD spectra in the same region (350 similar to 450 nm) were detected upon complex formation. They follow Lamb-Beer's law and exhibit isosbestic behavior. Both the UV-Vis and induced CD spectra of the antibody: porphyrin complex remain unchanged over a broad pH range ( pH 6 similar to 11), indicating remarkable stability of the complex and reflecting the dominant role of hydrophobic interaction between the hapten benzophenone and the antibody combining site.

Preparation of Pt nanoparticles assembled in multilayer films

PtCl62- anions were assembled on a glassy carbon electrode with [tetrakis(N-methylpyridyl)porphyrinato]cobalt cations through layer-by-layer method. then electrochemically reduced to yield zero valent Pt nanoparticles. Regular growth and surface morphology of the multilayer films were characterized by UV/vis. XPS and AFM.

Fabrication, patterning, and optical properties of nanocrystalline YVO4 : A (A = Eu3+, Dy3+, Sm3+, Er3+) phosphor films via sol-gel soft lithography

Nanocrystalline YVO4:A (A = Eu3+, Dy3+, Sm3+, Er3+) phosphor films and their patterning were fabricated by a Pechini sol-gel process combined with soft lithography. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric and differential thermal analysis (TG-DTA), atomic force microscopy (AFM) and optical microscopy, UV/vis transmission and absorption spectra, photoluminescence (PL) spectra, and lifetimes were used to characterize the resulting films. The results of XRD indicated that the films began to crystallize at 400 degreesC and the crystallinity increased with the increase of annealing temperatures. Transparent nonpatterned phosphor films were uniform and crack-free, which mainly consisted of grains with an average size of 90 nm. Patterned gel and crystalline phosphor film bands with different widths (5-60 mum) were obtained. Significant shrinkage and a few defects were observed in the patterned films during the heat treatment process. The doped rare earth ions (A) showed their characteristic emission in crystalline YVO4 phosphor films because of an efficient energy transfer from vanadate groups to them. The Sm3+ and Er3+ ions also showed upconversion luminescence in a YVO4 film host. Both the lifetimes and PL intensity of the rare earth ions increased with increasing annealing temperature from 400 to 800 degreesC, and the optimum concentration for Eu3+ was determined to be 7 mol % and those for Dy3+, Sm3-, and Er3+ were 2 Mol % of Y3- in YVO4 films, respectively.

Novel bipolar conjugated polymer containing both triphenylamine and oxadizole units

A novel bipolar conjugated polymer containing triphenylamine and 1, 3, 4-oxadiazole units was synthesized by Suzuki reaction. Its structure and properties were characterized by NMR, IR, UV-Vis, PL spectroscopy and electrochemical measurement. The photo luminescent spectroscopy and cyclic voltammograms measurement demonstrated that the resulting polymer shows blue emission (477 nm) and possesses both electron and hole-transporting property.

Synthesis of tetra-iron substituted sandwich-type pentadecatungstodiarsenate and its multilayers on glassy carbon electrode by self-assembly with electrocatalytic properties

A novel sandwich-type compound, Na-12 [Fe-4 (H2O)(2) (As2W15O56)(2)] . 38H(2)O (denoted as Fe(4)AS(4)W(30)) was synthesized. The compound was well characterized by means of IR, UV-Vis, W-138 NMR and elemental analyses. Redox electrochemistry of the compound has been studied in acid buffer solutions using cyclic voltammetry(CV). The compound containing multilayer films has been fabricated on the 4-aminobenzoic acid(4-ABA) modified glassy carbon electrode(GCE) surface by alternate deposition with a quaternized poly (4-vinylpyridine) partially completed with [Os(bpy)(2)Cl](2+/-) (denoted as QPVP-Os). CV, X-ray photoelectron spectroscopy (XPS) and UV-Vis spectroscopy were used to characterize the asprepared multilayer films. It is proved that the multilayer films are uniform and stable. The electrocatalytic activities of the multilayer films were investigated on the reduction of two substrates of important analytical interest, NO2- and H2O2.

Hydrothermal synthesis and characterization of bimetallic cluster complex [{Mn(phen)(2)}(2)V4O12]center dot 1/2 H2O

A new bimetallic cluster complex with the formula [(Mn(phen)(2))(2)V4O12].1/2 H2O has been synthesized through hydrothermal reaction of vanadate staring material with manganese cation in the presence of nitrogen donor chelating ligand and characterized by single-crystal X-ray diffraction, elemental analysis, IR UV-vis, ESR spectrum and thermal analysis. The compound crystallize in the monoclinic space group P2(1)/c with a = 18.475(4) Angstrom, b = 11.473(2) Angstrom, c = 23.667(5) Angstrom, beta = 97.76(3)degrees, V = 4971(2) Angstrom(3) and Z = 4. The structure of [{Mn(phen)(2)}(2)V4O12].1/2 H2O is composed of a discrete V4O124- cluster covalently attached to two [Mn(phen)(2)](2+) fragments.

Layer-by-layer multilayer films self-assembled from a rare-earth-containing poly-oxometalate Na-9[Eu(W5O18)(2)] and poly (allylamine hydrochloride) and their photoluminescent properties

Ultrathin multilayer films of a rare-earth-containing polyoxometalate Na-9[Eu(W5O18)(2)] (EW) and Poly (allyamine hydrochloride) (PAH) have been prepared by layer-by-layer self-assembly from dilute aqueous solutions. The fabrication process of the EW/PAH multilayer films was followed by UV-vis spectroscopy and ellipsometry, which show that the deposition process is linear and highly reproducible from layer to layer. An average EW/PAH bilayer thickness of ca. 2.1 nm was determine,by ellipsometry. In addition, the scanning electron microscopy (SEM) image of the EW/PAH film indicates that the film sufface is relatively uniform and smooth. The photoluminescent properties of these films were also investigated by fluoresence spectroscopy.

An organic-inorganic vanadium oxide with one-dimensional ladder-type structure: hydrothermal synthesis, structure and characterization of [V4O10(o-phen)(2)]

A novel organic-inorganic hybrid vanadium oxide [V4O10(o-phen)(2)], involving all vanadium atoms present in +5 oxidation, has been hydrothermally synthesized and characterized by elemental analysis, IR, UV-vis, ESR, XPS spectra and TG-DTA thermal analysis. The single-crystal X-ray diffraction shows that the red-brown crystal is formed in the triclinic system, space group P (1) over bar, a = 9.782(2), b = 6.5124(14), c = 19.765(4) Angstrom, alpha = 89.94(2)degrees, beta = 100.66(2)degrees, gamma = 89.86(2)degrees. The title compound exhibits an infinite one-dimensional ladder-type tetravanadate skeleton with organonitrogen donors of o-phenanthroline ligands coordinated directly to the vanadium oxide framework.