Void Geometry Driven Spin Crossover in Zeolite-Encapsulated Cobalt Tris(bipyridyl) Complex Ion

The cobalt(II) tris(bipyridyl) complex ion encapsulated in zeolite-Y supercages exhibits a thermally driven interconversion between a low-spin and a high-spin state-a phenomenon not observed for this ion either in solid state or in solution. From a comparative study of the magnetism and optical spectroscopy of the encapsulated and unencapsulated complex ion, supported by molecular modeling, such spin behavior is shown to be intramolecular in origin. In the unencapsulated or free state, the [Co(bipy)(3)](2+) ion exhibits a marked trigonal prismatic distortion, but on encapsulation, the topology of the supercage forces it to adopt a near-octahedral geometry. An analysis using the angular overlap ligand field model with spectroscopically derived parameters shows that the geometry does indeed give rise to a low-spin ground state, and suggests a possible scenario for the spin state interconversion.

Oxidation of aqueous sulfur dioxide catalyzed by poly-4-vinylpyridine-Cu(II) complex. Part 1: Homogeneous phase oxidation

The oxidation of aqueous sulfur dioxide in the presence of polymer-supported copper(II) catalyst is also accompanied by homogeneous oxidation of aqueous sulfur dioxide catalyzed by leached copper(II) ions. Aqueous phase oxidation of sulfur dioxide of low concentrations by oxygen in the presence of dissolved copper(II) has therefore been studied. The solubility of SO2 in aqueous solutions is not affected by the concentration of copper(II) in the solution. In the oxidation reaction, only HSO3- is the reactive S(IV) species. Based on this observation a rate model which also incorporates the effect of sulfuric acid on the solubility of SO2 is developed. The rate model includes a power-law type term for the rate of homogeneous phase reaction obtained from a proposed free-radical chain mechanism for the oxidation. Experiments are conducted at various levels of concentrations of SO2 and O-2 in the gas phase and Cu(II) in the liquid phase. The observed orders are one in each of O-2, Cu(II) and HSO3-. This suggests a first-order termination of the free radicals of bisulfite ions.

Structural, optical and electrical properties of sulfur-incorporated amorphous carbon films

Amorphous carbon-sulfur (a-C:S) composite films were prepared by vapor phase pyrolysis technique. The structural changes in the a-C:S films were investigated by electron microscopy. A powder X-ray diffraction (XRD) study depicts the two-phase nature of a sulfur-incorporated a-C system. The optical bandgap energy shows a decreasing trend with an increase in the sulfur content and preparation temperature. This infers a sulfur incorporation and pyrolysis temperature induced reduction in structural disorder or increase in sp (2) or pi-sites. The presence of sulfur (S 2p) in the a-C:S sample is analyzed by the X-ray photoelectron spectroscopy (XPS). The sp (3)/sp (2) hybridization ratio is determined by using the XPS C 1s peak fitting, and the results confirm an increase in sp (2) hybrids with sulfur addition to a-C. The electrical resistivity variation in the films depends on both the sulfur concentration and the pyrolysis temperature.

Preparation of Hexafluorodisilane and Reactions of Hexafluorodisilane and Hexachlorodisilane with Sulfur Trioxide

Hexafluorodisilane has been prepared by the fluorination of hexachlorodisilane or hexabromodisilane by potassium fluoride in boiling acetonitrile, in yields approximating 45 and 60% respectively. Hexafluorodisilane has been characterised by infrared spectral data, vapour density measurements and analytical data. Both hexafluorodisilane and hexachlorodisilane are found to react with sulfur trioxide when heated to 400°C for 12 h. The products of reaction are silicon tetrafluoride, silica and sulfur dioxide with hexafluorodisilane while hexachlorodisilane in addition gives rise to hexachlorodisiloxane.

Anomeric effect in sulfur-containing systems: An Ab-initio study

The anomeric effect in S---C---S and O---C---S systems was studied by using closed-shell Hartree-Fock theory. A comparison of the STO-3G level with the 4–31G and 6–31G* levels was performed for the O---C---O system, and the STO-3G level found adequate for study of the anomeric effect. Optimization of bond lengths and angles was conducted at the STO-3G level and limited studies were made at the 4–31G level. The nature of the torsional potential curves is compared for the O---C---O, O---C---S, and S---C---S systems. The possible reasons for the decreased anomeric effect in sulfur systems are discussed.

Low-Temperature Fluorination Of Sulfur-Compounds With Elemental Fluorine

Low temperature fluorination technique is adopted for fluorination of the following sulphur compounds in freon-11 medium (1) Sulphur dioxide (2) Thionyl chloride (3) Sulphuryl chloride (4) Tetrasulphur tetra nitride and (5) Sulphur bromide. All the compounds undergo oxidative fluorination to give rise to sulphur-fluorine compounds except sulphuryl chloride which resists fluorination. Sulphuryl chloride thus behaves as a good solvent medium for fluorination of other reactive compounds like elemental sulphur. Details of the experimental procedures adopted and the identification of the products will be presented

Synthesis of Thioesters from Carboxylic Acids via Acyloxyphosphonium Intermediates with Benzyltriethylammonium Tetrathiomolybdate as the Sulfur Transfer Reagent

An efficient protocol is reported for the synthesis of thioesters from carboxylic acids with use of acyloxy phosphonium salts as intermediates and benzyltriethylammonium tetrathiomolybdate as the sulfur transfer reagent.

Separation of sulfur-containing components of transfer ribonucleic acid on Bio-Gel P-2 and Sephadex G-10 columns

S-Labeled nucleosides of E. coli tRNA and some of the derivatives of thionucleosides were separated on Bio-Gel P-2 and Sephadex G-10 columns employing buffers of low salt concentration and high pH.

Synthesis of Thioesters by Simultaneous Activation of Carboxylic Acids and Alcohols Using PPh3/NBS with Benzyltriethylammonium Tetrathiomolybdate as the Sulfur Transfer Reagent

A new and simple route for the synthesis of thioesters starting from carboxylic acids and alcohols is reported by using tetrathiomolybdate as the key sulfur transfer reagent. Triphenylphosphane and N-bromosuccinimide were used for the activation of the carboxylic acid and alcohol in the same pot followed by the transfer of sulfur from tetrathiomolybdate. Thioesters were obtained in good to moderate yields. Primary alcohols show excellent reactivity and gave good yields of the corresponding thioesters, whereas secondary alcohols gave moderate yields and tertiary alcohols were very less reactive and gave poor yields of the corresponding thioesters.

Hydrophobic Peptide Channels and Encapsulated Water Wires

Peptide nanotubes with filled and empty pores and close-packed structures are formed in closely related pentapeptides. Enantiomorphic sequences, Boc-(D)Pro-Aib-Xxx-Aib-Val-OMe (Xxx = Leu, 1; Val, 2; Ala, 3; Phe, 4) and Boc-Pro-Aib-(D)Xxx-Aib-(D)Val-OMe ((XXX)-X-D = (D)Leu, 5; (D)Val, 6; (D)Ala, 7; (D)Phe, 8), yield molecular structures with a very similar backbone conformation but varied packing patterns in crystals. Peptides 1, 2, 5, and 6 show tubular structures with the molecules self-assembling along the crystallographic six-fold axis (c-axis) and revealing a honeycomb arrangement laterally (ab plane). Two forms of entrapped water wires have been characterized in 2: 2a with d(O center dot center dot center dot O) = 2.6 angstrom and 2b with d(O center dot center dot center dot O) = 3.5 angstrom. The latter is observed in 6 (6a) also. A polymorphic form of 6 (6b), grown from a solution of methanol-water, was observed to crystallize in a monoclinic system as a close-packed structure. Single-file water wire arrangements encapsulated inside hydrophobic channels formed by peptide nanotubes could be established by modeling the published structures in the cases of a cyclic peptide and a dipeptide. In all the entrapped water wires, each water molecule is involved in a hydrogen bond with a previous and succeeding water molecule. The O-H group of the water not involved in any hydrogen bond does not seem to be involved in an energetically significant interaction with the nanotube interior, a general feature of the one-dimensional water wires encapsulated in hydrophobic environements. Water wires in hydrophobic channels are contrasted with the single-file arrangements in amphipathic channels formed by aquaporins.

Fermi level depinning at the germanium Schottky interface through sulfur passivation

We demonstrate the depinning of Fermi level on both p- and n-type germanium after sulfur passivation by aqueous (NH4)(2)S treatment. Schottky contacts realized using metals with a wide range of work functions produce nearly ideal behavior confirming that the Fermi level is depinned. Examination of the passivated surface using x-ray photoelectron spectroscopy reveals bonding between Ge and sulfur.It is shown that good Ohmic contacts to n-type Ge and a hole barrier height (phi(Bp)) of 0.6 eV to p-type Ge can be achieved after this passivation treatment, with Zr Schottky contacts. This is the highest phi(Bp) reported so far.