Acid-catalyzed formation of hexahomooxacalix[3]arenes

The role of acid catalysis in oxacalix[3]arene synthesis has been investigated. A range of acids were used to optimize the yield of tert-butyloxacalix[3]arene, the most efficient being p-toluenesulfonic acid, which, with local symmetry complementary with that of the lower rim of the calixarene, provides a templating effect.     

Triiron and Triruthenium Carbonyl Clusters Bearing Bridging Long Chain Diphosphine and Capping Chalcogenido Ligands

Treatment of Ru₃(CO)₁₂ with dpphSe₂ (dpph = 1,6-bis(diphenylphosphino)hexane) in refluxing toluene in the presence of Me₃NO afforded two new compounds, Ru₃(CO)₇(-CO)(₃-Se)(-dpph) (1) and Ru₃(CO)₇(₃-Se)₂(-dpph) (2). A similar reaction of Ru₃(CO)₁₂ with dpppeSe₂ (dpppe = 1,5-bis(diphenylphosphino)pentane) gave exclusively Ru₃(CO)₇(₃-Se)₂(-dpppe) (3). Treatment of Ru₃(CO)₁₂ with dpphS₂ and dpppeS₂ at 110°C in the presence of Me₃NO afforded Ru₃(CO)₇(₃-S)₂(-dpph) (4) and Ru₃(CO)₇(₃-S)₂(-dpppe) (5), respectively. Reactions of Fe₃(CO)₁₂ with dpphSe₂ and dpppeSe₂, under identical conditions, afforded Fe₃(CO)₇(₃-Se)₂(-dpph) (6) and Fe₃(CO)₇(₃-Se)₂(-dpppe) (7), respectively. Compounds 1–7 were characterized spectroscopically and the molecular structures of compounds 1–4 were determined by single crystal X-ray crystallography. The core of 1 contains an equilateral triangle of ruthenium atoms with one capping selenium, one bridging dpph, one doubly bridging carbonyl and seven terminal carbonyl ligands. Complexes 2–4 have a square-pyramidal structure with two metal and two chalcogenide atoms alternating in the basal plane and the third metal atom at the apex of the pyramid, and belong to the family of well-known nido clusters with seven skeletal electron pairs.     

Synthesis, structures and reactivity of triosmium clusters containing terminal pyrazines, bridging hydroxy and methoxycarbonyl ligands

Four triosmium carbonyl clusters bearing terminal pyrazines, bridging hydroxy and methoxycarbonyl ligands of general formula [Os₃(CO)₉(μ-OH)(μ-OMeCO)L] (1, L = pyrazine; 2, L = 2-methylpyrazine; 3, L = 2,3-dimethylpyrazine; 4, L = 2,3,5-trimethylpyrazine) were synthesized by the reactions of [Os₃(CO)₁₂] with the corresponding pyrazine derivatives and water in the presence of a methanolic solution of Me₃NO in moderate yields. Compounds [Os₃(CO)₉(μ-OH)(μ-OMeCO)L] react with a series of two electron donor ligands, L′ at ambient temperature to give [Os₃(CO)₉(μ-OH)(μ-OMeCO)L′] (5, L′ = PPh₃; 6, L′ = P(OMe)₃; 7, L′ = ^tBuNC; 8, L′ = C₅H₅N) in good yields by the displacement of the pyrazine ligands. This implies that the pyrazine ligands in 1–4 are relatively labile. Compounds 2, 3, 4, and 8 were characterized by single crystal X-ray diffraction analyses. All the four compounds possess two metal–metal bonds and a non-bonded separation of two osmium atoms defined by Os(1)Os(3), which are simultaneously bridged by OH and MeOCO ligands and a heterocyclic ligand is terminally coordinated to one of the two non-bonded osmium atoms.     

Triosmium clusters derived from the reactions of thioureas with dodecacarbonyltriosmium: Crystal structures of [Os3(CO)11{η 1-SC(NMe2)2}], [Os3(CO)9(μ-OH)(μ-OMeOCO){η 1-SC(NMe2)2}] and [(μ-H)Os3(CO)9{μ 3-NHC(S)NH2}]

The reaction of [Os₃(CO)₁₂] with tetramethylthiourea in the presence of a methanolic solution of Me₃NO·2H₂O at 60° yields the compounds [Os₃(CO)₁₁{η ¹-SC(NMe₂)₂}] (1) in 56% yield and [Os₃(CO)₉(μ-OH)(μ-MeOCO){η ¹-SC(NMe₂)₂}] (2) in 10% yield in which the tetramethylthiourea ligand is coordinatedvia the sulfur atom at an equatorial position. Compound2 is a 50 e^? cluster with two metal-metal bonds and the hydroxy and methoxycarbonyl ligands bridging the open metal-metal edge. In contrast, the analogous reaction of [Os₃(CO)₁₂] with thiourea gives the compounts [(μ-H)Os₃(CO)₁₀{μ-NHC(S)NH₂}] (3) in 8% yield and [(μ-H)Os₃(CO)₉{₃-NHC(S)NH₂}] (4) in 30% yield. In3, the thioureato ligand bridges two osmium atomsvia the sulfur atom, whereas in4 in addition to the sulfur bridge, one of the nitrogen atoms of thioureato moiety bonds to the remaining osmium atom. The decacarbonyl compounds 3 can also be obtained in 50% yield from the reaction of [Os₃(CO)₁₀(MeCN)₂] with thiourea at ambient temperature. Compound3 converts to4 (65%) photochemically. Compound1 reacts with PPh₃ and acetonitrile at ambient temperature to give the simple substitution products [Os₃(CO)₁₁(PPh₃)] and [Os₃(CO)₁₁(MeCN)], respectively, while with pyridine, the oxidative addition product [(μ-H)Os₃(CO)₁₀(μ-NC₅H₄] is formed at 80°C. All the new compounds are characterized by IR,¹-H-NMR and elemental analysis together with the X-ray crystal structures of1,2 and4. Compound1 crystallizes in the triclinic space group P $P\bar 1$ with unit cell parametersa = 8.626(3) Å,b = 11.639(3) Å,c = 12.568(3_ Å,α = 84.67(2)°,β = 75.36(2)°,γ = 79.49(3)°,V = 1199(1) ų, andZ = 2. Least-squares refinement of 4585 reflections gave a final agreement factor ofR = 0.0766 (R _w = 0.0823). Compound2 crystallizes in the monoclinic space group P2_1/n with unit cell parametersa = 9.149(5) Å,b = 17.483(5) Å,c = 15.094(4) Å,β = 91.75(2)°,V = 2413(2) ų, andZ = 4. Least-squares refinement of 3632 reflections gave a final agreement factor ofR = 0.0603 (R _w = 0.0802). Compound4 crystallizes in the monoclinic space group C2/c with unit cell parametersa = 13.915(7) Å,b = 14.718(6) Å,c = 17.109(6) Å,β = 100.44(3)°,V = 3446(5) ų, andZ = 8. Least-squares refinement of 2910 reflections gave a final agreement factor ofR = 0.0763 (R _w = 0.0863).     

Preparation and characterization of conducting polyaniline layered magnetic nano composite polymer particles

Considering the application potentials of organic materials possessing both conducting and ferromagnetic functions in various electronic devices, an attempt was made to prepare conducting polyaniline (PANI) layered magnetic nano composite polymer particles. Two routes were used to modify magnetic Fe₃O₄ core particles. In one route, seeded emulsion polymerization of methyl methacrylate (MMA) was carried out in presence of nano‐sized Fe₃O₄ core particles. In another route, cross‐linker ethyleneglycol dimethacrylate (EGDM) was used in addition to MMA. The modified composite particles were named as Fe₃O₄/PMMA and Fe₃O₄/P(MMA‐EGDM), respectively. Finally, seeded chemical oxidative polymerization of aniline was carried out in the presence of Fe₃O₄/PMMA and Fe₃O₄/P(MMA‐EGDM) composite seed particles to obtain Fe₃O₄/PMMA/PANI and Fe₃O₄/P(MMA‐EGDM)/PANI composite polymer particles. The modification of Fe₃O₄ core particles was confirmed by electron micrographs, FTIR, UV–visible spectra, X‐ray photoelectron spectra, X‐ray diffraction pattern and thermogravimetric analyses. A comparative study showed that crosslinking of intermediate shell improved the magnetic susceptibility and electrical conductivity of PANI layered magnetic nano composite particles. Copyright © 2013 John Wiley & Sons, Ltd.     

Three-dimensional bundle-like multiwalled carbon nanotubes composite for supercapacitor electrode application

Bundle-type mutil-walled carbon nanotubes (MWCNTs) composite electrode is the first investigation and publication for the supercapacitor application. According to the thermogravimetric analysis results, as-synthesized BCNTs are considered as the electrode materials for supercapacitors and electrochemical double-layer capacitor in this study. The Brunauer–Emmett–Teller specific surface area of as-prepared bundled carbon nanotubes (BCNTs) is 95.29 m²/g given to a type III isotherm and H3 hysteresis loops. Slow scanning rates promote and enhance to achieve high C_b because of the superior conductivity of CNT bundles and one side close-layered Ni/Mg/Mo alloy inside the BCNT-based electrode and facile electron diffusivity between electrolyte and electrode. The specific capacitance C_s (1,560 F/g) is nearly equal to the maximum specific capacitance, which the BCNT-based composite electrode can actually be able to charge or fill in. The maximum energy density value is 195 Wh/kg with corresponding power density values of 0.21 kW/kg. Furthermore, the active 3D BCNTs material fabricated electrode enhances to contact the electrolyte directly and decreases the ion diffusion limitation. Electrochemical impedance spectroscopy spectrum summarized as the low-frequency area controls by mass transfer limitation, and the high-frequency area dominates by charge transfer of kinetic control. After 2,000 consecutive cyclic voltammetry sacnings and galvanostatic charge-discharge cycles at a current density of 1.67 A/g performs, the specific capacitance retentions of 3D BCNTs electrodes achieved 128.2 and 77.3%, respectively. Three-dimensional BCNT composite electrodes exhibit good conductivity and low charge transfer resistance, which is beneficial to fast charge transfer between the BCNTs electrode materials and electrolytes.     

Composite polymer particles prepared with different amounts of acrylic acid and their usefulness as carriers for biomolecules

Modification of surface properties of polymer particles suitable for biomedical application has been done by incorporating acrylic acid (AA) as a hydrophilic component. First, submicron-sized poly(methyl methacrylate) seed particles were prepared by soap-free emulsion polymerization. Then, seeded emulsion copolymerizations were carried out with varying proportions of AA and methyl methacrylate (MMA). MMA was used as a comonomer to prevent the dissolution of AA from the polymer particles. The adsorption behaviors of different biomolecules indicate that the surface of the composite polymer particles is sufficiently hydrophilic, particularly at higher AA content. Specific activities of adsorbed trypsin on the composite polymer particles were also comparatively high compared to free trypsin, which suggests that the adsorbed trypsin undergoes only slight conformational change owing to the interaction with the surface of particles.     

Three-photon excited PL spectroscopy and photo-generated Frenkel defects in wide-bandgap layered CdI2 semiconductors

We performed a three-photon excitation nonlinear photoluminescence (PL) spectroscopy in single crystals of wide-bandgap semiconductors (WBSs). The crystal temperature (TL)-dependent PL emission intensity (IPL) excited with different excitation power density (P) was measured. The PL emissions showed characteristics IPL with their maxima at around 520 nm. The IPL might be due to the presence of the photo-generated Frenkel defects (FDs) in WBSs. A detailed analysis of the PL spectra showed a third-order power law dependence of the maximum IPL on P for all the crystal temperature TL. The IPL was found to increase with decreasing TL. The results demonstrated the existence of the self-trapped excitons resulting from the presence of the FDs in the crystals.     

Band energy structure calculations and spin effect in zinc-blende semiconductors

Band energy structure of the n-doped zinc-blende semiconductor was calculated using norm-conserving pseudopotential and Green function methods. The calculations for the semiconductor with different dopant contents were performed in the presence of external circularly polarized axial and polar dc-field potentials. Changes in the spin density distribution for the clusters with different dopant concentrations and at different lattice temperatures and an enhancement of the spin-polarized delocalization states in the presence of the dc-field potential were observed. The observed photo-induced spin effects were explained within a framework of the band energy model of spin physics of taking into account of the photo-induced electron–phonon anharmonicity. The results are consistent with those obtained in experiments of photospintronics.     

Electronic-spin generation in multi-photon processes: Cubic anisotropy of pumping

We study the spin generation in multi-photon absorption processes in a bulk semiconductor, pumped it by a circularly polarized intense light by varying the angle of incidence. The generated spin polarization is calculated using the eight-band Kane model in the limit of large spin–orbit splitting and on the basis of the multi-photon photo-generation rate of the conduction electron spin density. It is found that the spin polarization strongly depends on the pumping photon energy outside the band edge. Cubic anisotropy in crystal pumping is also calculated. The results show that due to this anisotropy the spin generation differs by ∼8%, in consistence with earlier results obtained by others.