Synthesis and Properties of Stannole-Containing Polymers by Reaction of Bis(cyclopentadienyl)titanacyclopentadiene-Containing Polymers and Tin(IV) Chloride

Polymers having bis(cyclopentadienyl)titanacyclopentadiene units in the main chain were prepared by the polymerization of a low-valent bis(cyclopentadienyl)-titanium(II) complex, generated in situ from bis(cyclopentadienyl)titanium dichloride (Cp₂TiCl₂) and n-butyllithium (2 equiv), with internal diynes such as 1,4-bis(1-hexynyl)-benzene and 4,4′-bis(1-hexynyl)biphenyl. The bis(cyclopentadienyl)titanacyclopentadiene-containing polymers were subjected to the reaction with tin(IV) chloride, followed by the treatment with methyllithium to give 1,1-dimethylstannole-containing organometallic polymers in moderate yields. The stannole containing polymers are soluble in organic solvents, whose number-average molecular weight was estimated to be 2,700–2,800 by GPC. Optical and electrochemical properties of the resulting stannole-containing polymers were studied by their UV-vis spectra and cyclic voltammetric analyses, from which they were supposed to have low LUMO energy levels.     

Synthesis of Metal-containing Polymers via Ring Opening Metathesis Polymerization (ROMP). Part II: Polymers Containing Transition Metals

Following from Part I (this journal, 18(1), 2008), dedicated to main group metal containing polymers obtained by ROMP, the application of the same progressive concept to prepare polymers having this time transition metals in the side- or main-chain is here critically overviewed. These TMC polymers were produced through ROMP reactions promoted by Schrock’s Mo-carbene or the Grubbs’ Ru-carbene catalysts, the most recent and unique methodology for obtaining wished for structures. While discussing main aspects of these target-driven syntheses, as well as properties and applications of the neutral and cationic transition metal containing polymers, emphasis is laid upon organoiron macromolecules based on ferrocene scaffolds. Special attention is given to electrochemical behavior and thermal characteristics. Topics also cover polymers with other transition metals such as Co, Ni, Ru, Pd and Pt, which are important for generating zero valent metal nanoclusters in polymer films. Finally highlighted are some illustrative examples of metal-linked, metallodendrimers and hyperbranched, dendritic and star polymers.

Growth of SrTiO3 thin epitaxial films by aerosol MOCVD

SrTiO₃ thin films were prepared by aerosol metal-organic chemical vapour deposition on (001) MgO, R-plane Al₂O₃ and (001) Si single-crystal substrates. Strontium tetramethyl heptadionate and titanium n-butoxide dissolved in diethyleneglycol dimethyl ether were used as precursors. The structure of the films was investigated by X-ray diffraction and transmission electron microscopy. Epitaxial films with [001] and [111] orientation perpendicular to the substrate surface were obtained on MgO and Al₂O₃, respectively. The epitaxial films on the MgO substrate were found to be in a relaxed state with lattice parameters corresponding to the bulk values. SrTiO₃ films on the Si substrate were grown as highly textured in the [011]direction and randomly oriented in the plane parrallel to the substrate surface.     

Red polymer light-emitting devices based on an oxadiazole-functionalized europium(III) complex

A novel tris(dibenzoylmethanato)[5-(2-(4-tert-butylbenzenyl)-5-benzenyl-1,3,4-oxadiazole-4′)-1,10-phenanthroline]europium(III) [Eu(DBM)₃(BuOXD-Phen)] containing an electron-transporting oxadiazole-functionalized phenanthroline ligand was synthesized and characterized. Its UV–vis absorption and photoluminescence (PL), as well as the electroluminescence (EL) in polymer light-emitting devices (PLEDs) were investigated. The double-layer PLEDs with a configuration of ITO/PEDOT:PSS (50 nm)/PVK (40 nm)/PFO:PBD (30%):Eu(DBM)₃(BuOXD-Phen) (1–8 wt %) (80 nm)/Ba (4 nm)/Al (150 nm) were fabricated. Saturated red Eu³⁺ ion emission, based on the ⁵D₀ → ⁷F₂ transition, is centered at a wavelength of 614 nm with a full width at half maximum (FWHM) of 10 nm. The highest external quantum efficiency (QE_ext) of 1.26% at current density of 1.65 mA cm⁻², with a maximum brightness of 568 cd m⁻² at 137.8 mA cm⁻² was achieved from the device at 1 wt % dopant concentration.     

Growth of GaBN ternary solutions by organometallic vapor phase epitaxy

Layers of Ga_1-xB_xN with compositions from x = 0 to x = 0.07 were grown by organometallic vapor phase epitaxy on sapphire substrates using trimethylgallium, triethylboron (TEB) and NH₃ as precursors. Growth was done in the temperature range from 450 to 1000°C. The presence of boron was detected by the shift in the (0002) peak position in x-ray diffraction, by x-ray photoelectron spectroscopy, secondary ion mass spectrometry measurements, and by the changes in the band gap as measured by optical transmission. It was found that for the studied range of compositions the band gap varied from 3.4 eV for x = 0 to 3.63 eVfor x = 0.05. At certain TEB concentrations in the gas phase, the growth rate decreased abruptly, most likely because of a growth poisoning by the onset of growth of a very slow growing B-rich phase. The threshold TEB concentration for this growth poisoning decreased with increasing growth temperature; and at 1000°C, less than 1% of B could be incorporated as a result. GaBN alloys with about 7% substitutional boron were also produced by implantation of 5 × 10¹⁶ cm⁻² B ions at 60 keV into GaN, as evidenced by the shift of the band edge emission in cathodoluminescence spectra from 3.4 eV for GaN to 3.85 eV for GaBN.     

Photochemical preparation of aluminium oxide layers via vacuum ultraviolet irradiation of a polymeric hexanoato aluminium complex

By means of photochemical conversion of thin layers of a polymeric hexanoato aluminium complex as the precursor, thin aluminium oxide layers were prepared onto silicon wafers. The precursor compound was synthesized and characterized by several analytical techniques like NMR, FTIR, XPS, ICP, and found to be a polymeric aluminium-containing coordination compound which has been proposed to be a hydroxo-bridged aluminium chain with pendant hexanoyl side-chains ascertained as catena-poly[{di(κ-O,O-hexanoato)aluminium}(μ-hydroxo)] (PHAH). Thin layers deposited from a solution of PHAH in toluene onto silicon wafers were irradiated using VUV radiation from a xenon excimer lamp. The layers were characterized by XPS, XRD, XRR, and spectroscopic ellipsometry. VUV radiation with a radiant exposure of E = 36 J cm⁻² led to almost carbon-free amorphous layers with a composition close to that of alumina having a density of about 2.1 g cm⁻³. Thus, using the example of a polymeric aluminium complex, the potential of the photochemical conversion of metal complexes into oxides could be shown as an alternative method, in addition to sol–gel techniques, for the generation of thin plane metal-oxide layers at normal temperature and pressure.     

Effects of the concentrations of precursor and catalyst on the formation of monodisperse silica particles in sol–gel reaction

The monodispersed hybrid silica particles could be synthesized through the one-step sol–gel reaction with organosilane (3-mercaptopropyl trimethoxysilane, MPTMS) in aqueous solution. In this study, the effects of the concentrations of organosilane and the catalyst ((NH₄OH) on the formation of silica particles were investigated. For the first time we reported the successful one-step synthesis of monodisperse hybrid silica particles using organosilane chemicals in the previous study. In order to obtain better insight about the reaction processes, the silica particles were prepared in the presence of various concentrations of MPTMS and NH₄OH. On the basis of the experimental results, it was found that particle size increases as the concentration of organosilane increases. Also, as the concentration of catalyst increases, the diameter of these monodisperse particles decreases significantly. This research can contribute to a new broad avenue for the surface functionalization and hybrid material formation with various sizes.     

Synthesis and characterization of conductive copper-based metal-organic framework/graphene-like composites

Metal-organic framework (MOF) incorporating conductive graphene-like layers were synthesized and characterized. The selected MOF, HKUST-1, combines high surface area, water stability, simple preparation and low costs. Graphene-like layers incorporated into the MOF structure were obtained by a two-step oxidation/reduction wet treatment of a high surface carbon black. MOF composites were produced at different carbonaceous layers content. It was shown, through a wide characterization of the samples, that the composites preserve the main features of the parent MOF, additional exhibiting a tunable electrical conductivity.     

Synthesis and Microstructural Investigations of Organometallic Pd(II) Thiol-Gold Nanoparticles Hybrids

In this work the synthesis and characterization of gold nanoparticles functionalized by a novel thiol-organometallic complex containing Pd(II) centers is presented. Pd(II) thiol, trans, trans-[dithiolate-dibis(tributylphosphine)dipalladium(II)-4,4′-diethynylbiphenyl] was synthesized and linked to Au nanoparticles by the chemical reduction of a metal salt precursor. The new hybrid made of organometallic Pd(II) thiol-gold nanoparticles, shows through a single S bridge a direct link between Pd(II) and Au nanoparticles. The size-control of the Au nanoparticles (diameter range 2–10 nm) was achieved by choosing the suitable AuCl₄ ⁻/thiol molar ratio. The size, strain, shape, and crystalline structure of these functionalized nanoparticles were determined by a full-pattern X-ray powder diffraction analysis, high-resolution TEM, and X-ray photoelectron spectroscopy. Photoluminescence spectroscopy measurements of the hybrid system show emission peaks at 418 and 440 nm. The hybrid was exposed to gaseous NO _x with the aim to evaluate the suitability for applications in sensor devices; XPS measurements permitted to ascertain and investigate the hybrid –gas interaction.