Kinetics of Extraction of Iron(II1) by Bis(2-ethylhexyl Phosphate in a Laminar Liquid-Liquid Jet Reactor

The kinetics of iron(II1) extraction by bis(Zethylhexy1) phosphate (HDEHP, HA) in kerosene from sulfuric acid solutions has been studied in a liquid-liquid laminar jet reactor. The contact time of the interface in this reacting device is of the same order of magnitude as the surface renewal time in dispersion mixing and much less than that obtained in the relatively quiescent condition of the Lewis cell. Yet the analysis of the data in this study suggested a rate-controlling step involving surface saturation quite in conformity with that obtained in the Lewis cell and not with that in dispersion mixing as reported in the literature. Further, the mechanism suggested a weaker dependence of the rate on hydrogen ion concentration which was reported by other workers.

Synthesis, Reactivity, Structural Aspects, and Solution Dynamics of Cyclopalladated Compounds of N,N `,N `'-Tris(2-anisyl)guanidine

N,N',N `'-Tris(2-anisyl)guanidine, (ArNH)(2)C=NAr (Ar = 2-(MeO)C6H4), was cyclopallaclated with Pd(OC(O)R)(2) (R = Me, CF3) in toluene at 70 degrees C to afford palladacycles Pd{kappa(2)(C,N)-C6H3-(OMe)-3(NHC(NHAr)(=NAr))-2}(mu-OC(O)R)](2)(R = Me (1a) and CF3 (1b)) in 87% and 95% yield, respectively. Palladacycle 1a was subjected to a metathetical reaction with LiBr in aqueous ethanol at 78 degrees C to afford palladacycle Pd{kappa(2)(C,N)-C6H3(OMe)-3(NHC(NHAr)(=NAr))-2}(mu-Br)](2) (2) in 90% yield. Palladacycle 2 was subjected to a bridge-splitting reaction with Lewis bases in CH2Cl2 to afford the monomeric palladacycles Pd{kappa(2)(C,N)-C6H3(OMe)-3(NHC(NHAr)(=NAr))-2}Br(L)] (L = 2,6-Me2C5H3N (3a), 2,4-Me2C5H3N (3b), 3,5-Me2C5H3N (3c), XyNC (Xy = 2,6-Me2C6H3; 4a), (BuNC)-Bu-t (4b), and PPh3 (5)) in 87-95% yield. Palladacycle 2 upon reaction with 2 equiv of XyNC in CH2Cl2 afforded an unanticipated palladacycle, Pd{kappa(2)(C,N)-C(=NXy)(C6H3(OMe)-4)-2(N=C-(NH Ar)(2))-3} Br(CNXy)] (6) in 93% yield, and the driving force for the formation of 6 was ascribed to a ring contraction followed by amine-imine tautomerization. Palladacycles 1 a,b revealed a dimeric transoid in-in conformation with ``open book'' framework in the solid state. In solution, 1 a exhibited a fluxional behavior ascribed to the six-membered ``(C,N)Pd'' ring inversion and partly dissociates to the pincer type and kappa(2)-O,O'-OAc monomeric palladacycles by an anchimerically assisted acetate cleavage process as studied by variable-temperature H-1 NMR data. Palladacycles 3a,b revealed a unique trans configuration around the palladium with lutidine being placed trans to the Pd-C bond, whereas cis stereochemistry was observed between the Pd-C bond and the Lewis base in 4a (as determined by X-ray diffraction data) and 5 (as determined by P-31 and C-13 NMR data). The aforementioned stereochemical difference was explained by invoking relative hardness/softness of the donor atoms around the palladium center. In solution, palladacycles 3a-c exist as a mixture of two interconverting boat conformers via a planar intermediate without any bond breaking due to the six-membered ``(C,N)Pd'' ring inversion, whereas palladacycles 4a,b and 5 exist as a single isomer, as deduced from detailed H-1 NMR studies.

Stable Dispersions of Metal Oxide Nanowires and Nanoparticles in Water, Dimethylformamide and Toluene

In view of the important need to generate well-dispersed inorganic nanostructures in various solvents, we have explored the dispersion of nanostructures of metal oxides such as TiO2, Fe3O4 and ZnO in solvents of differing polarity in the presence of several surfactants. The solvents used are water, dimethylformamide (DMF) and toluene. The surfactant-solvent combinations yielding the best dispersions are reported alongwith some of the characteristics of the nanostructures in the dispersions. The surfactants which dispersed TiO2 nanowires in water were polyethylene oxide (PEO), Triton X-100 (TX-100), polyvinyl alcohol (PVA) and sodium bis(2-ethylhexyl) sulphosuccinate (AOT). TiO2 nanoparticles could also be dispersed with AOT and PEO in water, and with AOT in toluene. In DMF, PVA, PEO and TX-100 were found to be effective, while in toluene, only AOT gave good dispersions. Fe3O4 nanoparticles were held for long periods of time in water by PEO, AOT, PVA and polyethylene glycol (PEG), and by AOT in toluene. In the case of ZnO nanowires, the best surfactant-solvent combinations were found to be, PEO, sodium dodecyl sulphate (SIDS) and AOT in water and AOT, PEG, PVA, PEO and TX-100 in DMF In toluene, stable dispersions of ZnO nanowires were obtained with PEO. We have also been able to disperse oxide nanostructures in non-polar solvents by employing a hydrophobic silane coating on the surface.

Photophysics of conjugated polymers: interplay between Forster energy migration and defect concentration in shaping a photochemical funnel in PPV

Recent single molecule experiments have suggested the existence of a photochemical funnel in the photophysics of conjugated polymers, like poly[2-methoxy-5-(2'-ethylhexyl)oxy-1,4-phenylenevinylene] (MEH-PPV). The funnel is believed to be a consequence of the presence of conformational or chemical defects along the polymer chain and efficient non-radiative energy transfer among different chromophore segments. Here we address the effect of the excitation energy dynamics on the photophysics of PPV. The PPV chain is modeled as a polymer with the length distribution of chromophores given either by a Gaussian or by a Poisson distribution. We observe that the Poisson distribution of the segment lengths explains the photophysics of PPV better than the Gaussian distribution. A recently proposed version of an extended particle-in-a-box' model is used to calculate the exciton energies and the transition dipole moments of the chromophores, and a master equation to describe the excitation energy transfer among different chromophores. The rate of energy transfer is assumed to be given here, as a first approximation, by the well-known Forster expression. The observed excitation population dynamics confirms the photochemical funneling of excitation energy from shorter to longer chromophores of the polymer chain. The time scale of spectral shift and energy transfer for our model polymer, with realistic values of optical parameters, is in the range of 200-300 ps. We find that the excitation energy may not always migrate towards the longest chromophore segments in the polymer chain as the efficiency of energy transfer between chromophores depends on the separation distance between the two and their relative orientation.

Comparison of CVD and MOCVD-grown Al2O3 coatings in the performance of cemented carbide cutting tool inserts

Low-pressure MOCVD, with tris(2,4 pentanedionato)aluminum(III) as the precursor, was used in the present investigation to coat alumina on to cemented carbide cutting tools. To evaluate the MOCVD process, the efficiency in cutting operations of MOCVD-coated tools was compared with that of tools coated using the industry-standard CVD process.Three multilayer cemented carbide cutting tool inserts, viz., TiN/TiC/WC, CVD-coated Al2O3 on TiN/TiC/WC, and MOCVD-coated Al2O3 on TiN/TiC/WC, were compared in the dry turning of mild steel. Turning tests were conducted for cutting speeds ranging from 14 to 47 m/min, for a depth of cut from 0.25 to 1 mm, at the constant feed rate of 0.2 mm/min. The axial, tangential, and radial forces were measured using a lathe tool dynamometer for different cutting parameters, and the machined work pieces were tested for surface roughness. The results indicate that, in most of the cases examined, the MOCVD-coated inserts produced a smoother surface finish, while requiring lower cutting forces, indicating that MOCVD produces the best-performing insert, followed by the CVD-coated one. The superior performance of MOCVD-alumina is attributed to the co-deposition of carbon with the oxide, due to the very nature of the precursor used, leading to enhanced mechanical properties for cutting applications in harsh environment.

Gas Sensing Properties of Tin Oxide Powder Synthesized in the Presence of Surfactants

Nanocrystalline tin oxide powder was prepared using a solution precipitation technique after adding the surfactant sodium bis (2-ethylhexyl) sulfosuccinate (AOT). Powders were characterized using X-ray diffraction (XRD), surface area (BET) and transmission electron microscopy (TEM). The gas sensitivity for surfactant added powders increased for liquid petroleum gas (LPG) as well as compressed natural gas (CNG), due to the decreased particle size and the increased surface area. The LPG gas sensitivity increased several times using phosphorus treated surfactant AOT.

Influence of Side-Chain on Structural Order and Photophysical Properties in Thiophene Based Diketopyrrolopyrroles: A Systematic Study

In this work, we have synthesized a series of TDPP derivatives with different alkyl groups such as n-hexyl (-C6H13) 3a, 2-ethylhexyl (-(2-C2H5)C6H12) 3b, triethylene glycol mono methyl ether (-(CH2CH2O)(3c)H-3, TEG) 3c, and octadodecyl (-(8-C8H17)C12H22) 3d. N,N dialkylation of Othiophene-diketopyrrolopyrrole (TDPP, 1) strongly influences its solubility, solid state packing, and structural order. These materials allow us to explicitly study the influence of alkyl chain on solid state packing and photophysical properties. TDPP moiety containing two different alkyl groups 3e (TEG and 2-ethylhexyl) and 3f (TEG and n-hexyl) were synthesized for the first time. The absorption spectra of all derivatives exhibited a red shift in solid state when compared to their solution spectra. The type of alkyl chains leads to change in the optical band gaps in solid state. The fluorescence study reveals that TDPP derivatives have strong pi-pi interaction in the solid state and the extent of bathochromic shift is due to combination of intramolecular interaction and formation of aggregates in solid state. This behavior strongly depends on the nature of alkyl chain. The presence of strong C-H center dot center dot center dot O inter chain interactions and CH-pi interactions in solid state exhibits strong influence on the photophysical properties of TDPP chromophore.

Polymer solar cells: design of materials by donor-acceptor approach

A brief overview of our group research activities is given and the concept of donor acceptor is described for the development of conjugated polymers for optoelectronic devices. In particular, a new family of conjugated polymers based on dithienopyrrole has been synthesized to demonstrate the concept of donor-acceptor. The dithienopyrrole was coupled to benzodithiophene via Stille coupling to obtain two low band gap polymers P5a and P5b having -C18H37 and -2-ethylhexyl alkyl chain respectively. Both the polymers exhibit absorption within the solar spectrum with an optical band gap below 2 eV. Atomic force microscopy revealed that both the polymers form smooth film with roughness of 2.4 nm and photoluminescence measurement of polymer/fullerene derivative blend film suggests effective dissociation of exciton.

Hydrogen-Bond-Driven Controlled Molecular Marriage in Covalent Cages

A supramolecular approach that uses hydrogen-bonding interaction as a driving force to accomplish exceptional self-sorting in the formation of imine-based covalent organic cages is discussed. Utilizing the dynamic covalent chemistry approach from three geometrically similar dialdehydes (A, B, and D) and the flexible triamine tris(2-aminoethyl)amine (X), three new 3+2] self-assembled nanoscopic organic cages have been synthesized and fully characterized by various techniques. When a complex mixture of the dialdehydes and triamine X was subjected to reaction, it was found that only dialdehyde B (which has OH groups for H-bonding) reacted to form the corresponding cage B3X2 selectively. Surprisingly, the same reaction in the absence of aldehyde B yielded a mixture of products. Theoretical and experimental investigations are in complete agreement that the presence of the hydroxyl moiety adjacent to the aldehyde functionality in B is responsible for the selective formation of cage B3X2 from a complex reaction mixture. This spectacular selection was further analyzed by transforming a nonpreferred (non-hydroxy) cage into a preferred (hydroxy) cage B3X2 by treating the former with aldehyde B. The role of the H-bond in partner selection in a mixture of two dialdehydes and two amines has also been established. Moreover, an example of unconventional imine bond metathesis in organic cage-to-cage transformation is reported.

Experimental determination and theoretical correlation for the solubilities of dicarboxylic acid esters in supercritical carbon dioxide

The synthesis of high molecular weight esters such as bis (2-ethylhexyl) sebacate is of significance for its use as a lubricant. This ester is synthesized by the transesterification of dimethyl sebacate with 2-ethylhexanol. Therefore, the solubilities of bis (2-ethylhexyl) sebacate and dimethyl sebacate were determined at 308-328 K at pressures of 10-18 MPa in supercritical carbon dioxide. The solubility of dimethyl sebacate was always higher than bis (2-ethylhexyl) sebacate at a given temperature and pressure. The Mendez-Teja model was used to verify the self-consistency of data. Further, a new semi-empirical model with three parameters was developed using the solution theory coupled with Wilson activity coefficient. This model was used to correlate the experimental data of this work and solubilities of many high molecular weight esters reported in the literature. (C) 2015 Elsevier B.V. All rights reserved.

Tris(methyl 3-oxobutanoato-kappa O-2,O `)aluminium(III)

In the title compound, [Al(C5H7O3)(3)],three acac-type ligands(methyl 3-oxobutanoate anions) chelate to the aluminium(III)cation in a slightly distorted AlO6 octahedral coordination geometry.Electron delocalization occurs within the chelating rings.

Tris(tert-butyl 3-oxobutanoato-kappa O-2(1),O- )-aluminium(III) at 153 K

In the title complex, [Al(C8H13O3)(3)], a potential metal-organic chemical vapour deposition (MOCVD) precursor, three bidentate ligand molecules are bound to the metal atom, forming an octahedral geometry. Two non-planar six-membered chelate rings adopt screw-boat conformations, while the third ring has a conformation that lies about halfway between an envelope and a screw-boat.

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.

NMR-Studies of Octahedral Dicyano-(2,2' Bipyridine) and Tetracyano-(2,2'-Bipyridine) Iron(ii) Complexes

Coordination compounds of the polypyridines, 2,2 ' -bipyridine (bipy) and 1,10-penanthroline (phen) have offered renewed interest on account of their manifold applications and from the point of view of understanding their structure-reactivity relationships.1 Iron(II) reacts with them to form tris-complexes possessing spin-paired ground states. Cyanide ion greatly enhances the rate of displacement of bipy or phen to form the Schilt class of compounds. Fe(bipy)2(CN)2 and Fe(phen)2(CN)2. They display varying colours in solution depending upon the nature of the solvent and react reversibly with acids to form diprotonated species.2 Magnetic circular dichroism studies have been reported to describe their lowest electronic excitation.