Synthesis of Azo Coupled Crown Ethers Containing Transition Metal and other Chromophoric Environments and Their Ion Complexation Properties

The crown ethers, 2,3-benzo-1,4,7,10,13-pentaoxa-cyclopentadeca-2-ene and 2,3, ll,12-dibenzo-l,4,7,10,13,16-hexaoxscyclooctadeca-2,11-diene are incorporated into H,N'-ethylenebis(acetylacetoneimino) nickel(II) and copper(II), phenol, and β-naphthol by diazo coupling reactions. The selective nature of the coupling reaction has-been demonstrated by the isolation of both asymmetric mono- and symmetric bis(glyoxalarylcrownhydrazoneimino) metal(II) complexes. An interesting binuclear complex containing two intramolecularly rearranged (glyoxal-hydrazonearylimino) metal(II) groups joined by 18-crown-6 result8 when bis(arenediazonium)-18-crown-6 is coupled with the metal(I1) Schiff bases. The substituted ethers form cationic salts with NaClO4, KCNS, NH4CNS, 14g(CNS)2 and Ca(CNS)2. All the synthesised ethers exhibit ion selectivity sequence as K+ > Na+ and Ca2+ > Mg2+.

Investigation of surface activity and photoinduced diffusion of metals in solution deposited amorphous films of As2S3

Surface activity of solution deposited (SD) amorphous films of As2S3 has been investigated. Silver and copper are readily deposited on such films from appropriate aqueous ionic solutions. The metals diffuse into the films upon irradiation with energetic photons. Structure and properties of SD films have been investigated using electron microscopy, optical spectroscopy and differential scanning calorimetry. The amorphous films tend to crystallize upon metal diffusion. The stability of amorphous films, the deposition of metals on their active surfaces and the photo-induced diffusion may all be attributed to the presence or production of charged defects in amorphous chalcogenide films.

Vibrational spectra and ferroelectric transition in sodium ammonium selenate dihydrate

The Raman and infrared absorption spectra of sodium ammonium selenate dihydrate (SASD) have been recorded both above and below the ferroelectric transition temperature. The deuterated SASD has also been investigated. The results support the view that while there is only one type of NH4+ ions in the para electric phase, there are two types of NH4+ ions below Tc. The water molecules undergo considerable change and non-equivalent O-H bonds are produced below Tc. The SeO2/4- ions undergo very little change.

Phase transition in malonic acid: An infrared study

Malonic acid is shown to undergo an interesting phase transition at 360 K when the two non-equivalent cyclic hydrogen-bonded dimers present in the low-temperature phase become equivalent.

Molecularly adsorbed oxygen on metals: electron spectroscopic studies

Oxygen is shown to adsorb molecularly on gold as well as on Ag and Pt. UV and X-ray photoelectron spectroscopy and Auger electron spectroscopy have been employed to investigate electron states of molecularly adsorbed oxygen.

Structural phase transition study of the morphotropic phase boundary compositions of Na0.5Bi0.5TiO3-PbTiO3

Neutron, synchrotron x-ray powder diffraction and dielectric studies have been performed for morphotropic phase boundary (MPB) compositions of the (1 - x )Na1/2Bi1/2TiO3-xPbTiO(3) system. At room temperature, the MPB compositions (0.10 < x <= 0.15) consist of a mixture of rhombohedral (space group R3c) and tetragonal ( space group P4mm) structures with the fraction of tetragonal phase increasing with increasing PbTiO3 content. On heating, while the rhombohedral phase just outside the MPB region, i.e. x = 0.10, transforms directly to a cubic phase, the rhombohedral phase of the MPB compositions transforms gradually to a tetragonal phase, until interrupted by a rhombohedral-cubic phase transition. The correspondence of the dielectric anomalies with the structural transitions of the different compositions has been examined and compared with earlier reports.

Behaviour of ultrasonic velocities in amorphous Se90Ge10 and Se85Ge15 alloys near their glass transition

Precise measurements of 10 MHz frequency longitudinal and shear wave velocities are reported in amorphous SeGe alloys near their glass transition temperature T g . There is a sharp decrease of the velocities near T g , but the reduction in velocities appears smaller than expected.

Pressure and alloying effects on the metal to insulator transition in NiS2-xSex studied by infrared spectroscopy

The metal to insulator transition in the charge-transfer NiS2-xSex compound has been investigated through infrared reflectivity. Measurements performed by applying pressure to pure NiS2 (lattice contraction) and by Se alloying (lattice expansion) reveal that in both cases an anomalous metallic state is obtained. We find that optical results are not compatible with the linear Se-alloying vs pressure-scaling relation previously established through transport, thus pointing out the substantially different microscopic origin of the two transitions.

Rare earth transition metal sulfides, LnMS3

Ternary rare earth transition metal sulfides LnMS3 with Ln = La, Nd, and Gd, and M = V and Cr; as well as Ln = La and M = Mn, Fe, Co, and Ni have been prepared and characterized. The vanadium and chromium sulfides crystallize in a monoclinic layer structure isotypic with LaCrS3, while the other LnMS3 sulfides crystallize in a hexagonal structure. Chemical shifts of the metal K-absorption edge and XPS binding energies of core levels indicate that the transition metal is trivalent in the V and Cr sulfides, while it is divalent in the Mn, Fe, Co, and Ni sulfides. Electrical and magnetic properties of the sulfides are discussed in terms of their structures and the electronic configurations of the transition metal ions.

An XPS study of the surface oxidation states of metals in some oxide catalysts

Calcined samples of chromia supported on Al2O3, ZnO, or SnO2 show both Cr(VI) and Cr(III) on the surface, Cr(VI) being preponderant in the case of Al2O3-supported catalysts. The proportion of Cr(VI) decreases with increase in Cr content of the calcined catalysts. Reduction of the supported chromia catalysts in H2 at 720 K for 1 hr gives rise to Cr(III) and Cr(V). On carrying out the dehydrogenation of cyclohexane on the chromia catalysts a higher proportion of Cr(V) is found than after treatment with hydrogen. Vanadia supported on Al2O3 or MoO3 shows significant proportion of V(IV) on carrying out the oxidation of toluene on the catalysts. Calcined MoO3 (10%)/Al2O3 shows only Mo(VI) on the surface at 300 K, but on heating to 670 K in vacuum shows the presence of a considerable proportion of Mo(V) which on cooling disproportionates to Mo(IV) and Mo(VI). Mo(V) is noticed on surfaces of this catalyst on reduction with hydrogen as also on carrying out dehydrogenation of cyclohexane. While Bi2MoO6 shows only Mo(VI) on the surface at 300 K, heating it to 670 K in vacuum changes it entirely to Mo(V) which then gives rise to Mo(IV) and Mo(VI) on cooling.

Preparation and thermal stability of trioxalatocobaltates of bivalent metals KM2+ [Co(C2O4)3]·xH2O

Trioxalatocobaltates of bivalent metals KM2+[Co(C2O4)3]·x H2O, with M2+ = Ba, Sr, Ca and Pb, have been prepared, characterized and their thermal behaviour studied. The compounds decompose to yield potassium carbonate, bivalent metal carbonate or oxide and cobalt oxide as final products. The formation of the final products of decomposition is influenced by the surrounding atmosphere. Bivalent metal cobaltites of the types KM2+CoO3 and M2+CoO3—x are not identified among the final products of decomposition. The study brings out the importance of the decomposition mode of the precursor in producing the desired end products.

Synthesis of Azo Coupled Crown Ethers Containing Transition Metal and other Chromophoric Environments and Their Ion Complexation Properties

The crown ethers, 2,3-benzo-1,4,7,10,13-pentaoxa-cyclopentadeca-2-ene and 2,3, ll,12-dibenzo-l,4,7,10,13,16-hexaoxscyclooctadeca-2,11-diene are incorporated into H,N'-ethylenebis(acetylacetoneimino) nickel(II) and copper(II), phenol, and β-naphthol by diazo coupling reactions. The selective nature of the coupling reaction has-been demonstrated by the isolation of both asymmetric mono- and symmetric bis(glyoxalarylcrownhydrazoneimino) metal(II) complexes. An interesting binuclear complex containing two intramolecularly rearranged (glyoxal-hydrazonearylimino) metal(II) groups joined by 18-crown-6 result8 when bis(arenediazonium)-18-crown-6 is coupled with the metal(I1) Schiff bases. The substituted ethers form cationic salts with NaClO4, KCNS, NH4CNS, 14g(CNS)2 and Ca(CNS)2. All the synthesised ethers exhibit ion selectivity sequence as K+ > Na+ and Ca2+ > Mg2+.

Reaction of sulphuryl chlorofluoride with a few metals and metal oxides

Sulphuryl chlorofluoride has no observable reaction with metals and metal oxides at room temperature. Metals like copper, silver, iron, and zinc react with the chlorofluoride in the temperature range 200–400°C. Metal chlorides, metal fluorides and sulphur dioxide are the main products of these reactions. With the corresponding metal oxides, on the other hand, the respective metal sulphates are formed in addition to the metal chlorides and fluorides. In the case of lead and lead oxide, lead chlorofluoride is formed instead of lead chloride and lead fluoride. Sulphuryl fluoride is formed in small quantities in all these reactions by the decomposition of the chlorofluoride. Glass is not attacked by sulphuryl chlorofluoride below 500°C.

Mechanics of transition in an axisymmetric laminar boundary layer on a circular cylinder

Measurements of the growth of artificially generated turbulent spots and intermittency distribution in the transition region on a circular cylinder in axial flow show that the instability Reynolds number of 11,000 has a marked effect on the properties. In particular, it is found that the spot production in the initial region when a single turbulent spot has not yet wrapped around the cylinder and the propagation is essentially two-dimensional, is significantly altered. But the transition in the downstream or latter region, where most of the turbulent spots propagate onedimensionally (like the turbulent plugs in a pipe), is not affected. When the radius Reynolds number is more than 11,000, the intermittency law in the initial region is essentially the same as in twodimensional flow on a flat plate and in the latter region it is the one-dimensional flow in a pipe, the demarcation between the two regions being quite sharp.

Structure and Bonding in N-Methylacetamide Complexes of Alkali and Alkaline Earth Metals

A detailed crystallographic investigation of N-methylacetamide complexes of Li, Na, K, Mg and Ca has been made in view of its importance in the coordination chemistry and biochemistry of alkali and alkaline earth metals. The metal ions bind to the amide oxygen causing an increase in the carbonyl distance and a proportionate decrease in the central C-N bond distance. The decrease in the central C-N distance is accompanied by an increase in the distance of the adjacent C-C bond and a decrease in the adjacent C-N bond distance. The metal ion generally deviates from the direction of the lone pair of the carbonyl oxygen and also from the plane of the peptide, the out-of-plane deviation varying with the ionic potential of the cation. The metal-oxygen distance in alkali and alkaline earth metal complexes of a given coordination number also varies with the ionic potential of the cation, as does the strength of binding of the cations to the amide. The amide molecules are essentially planar in these complexes, as expected from the increased bond order of the central C-N bond. The NH bonds of the amide are generally hydrogen bonded to anions. The structures of the amide complexes are compared with those of other oxygen donor complexes of alkali and alkaline earth metals. The structural study described here also provides a basis for the interpretation of results from spectroscopic and theoretical investigations of the interaction of alkali and alkaline earth metal cations with amides.