Photoisomerisation in Aminoazobenzene‐Substituted Ruthenium(II) Tris(bipyridine) Complexes: Influence of the Conjugation Pathway

Transition‐metal complexes containing stimuli‐responsive systems are attractive for applications in optical devices, photonic memory, photosensing, as well as luminescence imaging. Amongst them, photochromic metal complexes offer the possibility of combining the specific properties of the metal centre and the optical response of the photochromic group. The synthesis, the electrochemical properties and the photophysical characterisation of a series of donor–acceptor azobenzene derivatives that possess bipyridine groups connected to a 4‐dialkylaminoazobenzene moiety through various linkers are presented. DFT and TD‐DFT calculations were performed to complement the experimental findings and contribute to their interpretation. The position and nature of the linker (ethynyl, triazolyl, none) were engineered and shown to induce different electronic coupling between donor and acceptor in ligands and complexes. This in turn led to strong modulations in terms of photoisomerisation of the ligands and complexes.     

Selective extraction of iron(III) from aqueous nitrate solution in the presence of cobalt(II), copper(II) and nickel(II) ions using bis(delta2-2-imidazolinyl)-5,5'-dioxime.

The feasibility of using bis(delta2-2-imidazolinyl)-5,5'-dioxime (H2L) for the selective extraction of iron(III) from aqueous solutions was investigated by employing an solvent-extraction technique. The extraction of iron(III) from an aqueous nitrate solution in the presence of metal ions, such as cobalt(II), copper(II) and nickel(II), was carried out using H2L in binary and multicomponent mixtures. Iron(III) extraction has been studied as a function of the pH, equilibrium time and extractant concentration. From the extracted complex species in the organic phase, iron(III) was stripped with 2 M HNO3, and later determined using atomic-absorption spectrometry. The extraction was found to significantly depend on the aqueous solution pH. The extraction of iron(III) with H2L increases with the pH value, reaching a maximum in the zone of pH 2.0, remaining constant between 2 and 3.5 and subsequently decreasing. The quantitative extraction of iron(III) with 5 x 10(-30 M H2L in toluene is observed at pH 2.0. H2L was found to react with iron(III) to form ligand complex having a composition of 1:2 (Fe:H2L).     

Composition spread metal thin film fabrication technique based on ion beam sputter deposition

A composition spread metal thin film fabrication technique based on ion beam sputter deposition method was developed. The technique enables us to fabricate any desired part or a complete binary/ternary composition spread metal thin films onto a single substrate by sequentially sputtering different target materials. Composition spread metal thin films can be deposited directly on a dielectric film in patterned electrode shape for C-V and I-V measurements. The system could be especially useful in the search for new multi-component metal gate materials.     

Schottky metal library for ZNO-based UV photodiode fabricated by the combinatorial ion beam-assisted deposition

A binary alloy Schottky barrier diode on zinc oxide (ZnO) was developed using the combinatorial ion beam-assisted deposition system. The compositional fraction of the binary alloy was continuously varied using the composition-spread technique, to control the Schottky barrier height. After metal deposition, patterned Schottky diodes were fabricated on a ZnO single-crystal substrate. Pt-Ru alloy was selected from the work function viewpoint. Our experiments showed that the compositional fraction of the Schottky binary alloys changed continuously as designed and the Schottky barrier heights measured by current-voltage (I-V) measurements increased with increasing Pt content. Maximum barrier height difference for ZnO was 137 meV. Using ion beam deposition in parallel with the combinatorial system showed that the Schottky barrier heights for ZnO can be controlled by binary metal alloying.     

Construction of nonanuclear supramolecular structures from simple modular units

A porphyrazine based supramolecule with a nonanuclear structure has been prepared by the ready coordination of pyridine donor sites in octakis(4-pyridoxyethylthio)porphyrazinatomagnesium with vanadyl bis(acetylacetonate) and characterized by EPR spectroscopy.     

Lavandulifolioside: A New Phenylpropanoid Glycoside from Stachys lavandulifolia

A new phenlypropanoid glycoside has been isolated from the methanolic extract of the aerial parts of Stachys lavandulifolia (Lamiaceae), lavandulifolioside (1) . On the basis of chemical and spectral data the structure of the new compound 1 has been elucidated as β-(3,4-dihydroxyphenyl)ethyl O-α-L -arabinopyranosyl-(1→2)-α-L -rhamnopyranosyl-(1→3)-4-O-caffeoyl-β-D -glucopyranoside.     

Ascorbic acid as a potential masking agent in the tanning process. Olated chromium complexes involving ligating ascorbate and bridging sulfate groups

Two polynuclear complexes, a dimer and a tetramer, involving sulfate and hydroxo bridges and ligating ascorbate were isolated from aqueous solutions. Structural formulae are proposed on the basis of microanalytical and thermal analysis results, i.r., ¹³C-n.m.r., mass spectral data and magnetic measurements.     

Oxygen/nitrogen ordering in lanthanum new phase (La3Si8N11O4)

High-resolution ¹⁷O NMR spectra have been collected for crystalline samples of lanthanum new phase, La₃Si₈N₁₁O₄. In conjunction with previously published ²⁹Si and ¹⁵N spectra obtained for this phase, and in the light of the high-quality crystal structure data reported recently, a more detailed interpretation of the NMR spectra is presented than was possible in previous studies. The non-bridging oxygens in the structure are responsible for the single sharp peak seen in the ¹⁷O spectrum at 188 ppm; the remaining oxygens, occupying bridging sites shared with nitrogen, show up only weakly on the ¹⁷O spectrum as a broad diffuse band centered around zero ppm. The peak at −57.3 ppm on the ²⁹Si spectrum is believed to correspond to an overlap of [SiN₄] and [SiON₃] environments, with the −68.2 ppm peak corresponding to an [SiO₂N₂] environment.     

Modification of the cation exchange resin properties by impregnation in polyethyleneimine solutions: application to the separation of metallic ions

A commercial cation exchange resin Amberlite 200 has been modified after immersion in solutions of polyethyleneimine (PEI). The kinetic of fixation of the metallic ions have been determined. The modification of the surface of the resin deals with a change in the order of the affinities of the resins towards cations. The retention is the function of the formation and the stability of the complex. The conditions of modification (pH, PEI concentration and time of immersion) have been examined and the modification was confirmed by the determination of the exchange capacities, the distribution coefficient (P) and the selectivity factors (S). The obtained results revealed the effect of PEI on the exchange properties of the resin. The pH range selected (6-8) permitted a good adherence of PEI onto the resin surface. The quantity of the adsorbed PEI was increased by raising the initial concentration and the immersion period. The exchange capacity for copper ion passed from 2.6 mmol g⁻¹, in the case of unmodified resin, to 3.9 mmol g⁻¹ for the modified one.     

Preparation of hollow beads of poly(styrene-co-divinyl benzene)

Two methods are described for the production of hollow beads by copolymerization of styrene and divinyl benzene. Characterization of the beads is described and growth mechanisms proposed.