Growth and microstructural studies of some indium chalcopyrite semiconductors

Single crystals of ternary chalcopyrite semiconductors such as CuInS₂, CuInSe₂, CuInTe₂, and CuInSSe, a pseudo-ternary semiconductor, have been grown by Chemical Vapour Transport (CVT) technique using iodine as the transporting agent. Microstructural analysis was carried out with the help of Scanning Electron Microscope (SEM) and optical microscope for the grown single crystals.     

Growth and Characterisation of Pure and Nickel-doped Strontium Tartrate Tetrahydrate Single Crystals

Strontium tartrate tetrahydrate single crystals doped with nickel have been grown in silica gel. The grown crystals have been characterized by X-ray, atomic absorption spectroscopy (AAS), thermogravimetric analysis (TGA), and etching technique.     

Periodic Crystallisation of Magnesium Hydroxide in Agar-Agar Gel

Investigations are made to get the experimental conditions for obtaining periodic crystallisation of magnesium hydroxide in agar-agar gel. A detailed study is made on the dependence of the velocity constant (K), the spacing coefficient \documentclass{article}\pagestyle{empty}\begin{document}$ \left( {p = \frac{{x_{n + 1} }}{{x_n }}} \right)'$\end{document} the length of the continuous precipitate and the width of the rings on the concentrations of the inner and outer electrolytes. Using SHINOHARA 's revised coagulation theory, the flocculation value F is calculated. F = Γ + C₃₀, where Γ is the characteristic concentration of the outer electrolyte for which the flocculation starts and C₃₀ is the reduced concentration of the reaction product. The value of the concentration of the outer electrolyte for which the flocculation stops (γ) is calculated. The dependence of F on the concentrations of the reactants is also discussed. Observation of a coneshaped precipitation is also reported.     

Synthesis,growth of single crystals and their characterization: l-Alaninium maleate (LAM)

In recent days amino acid single crystals are gaining importance due to good optical behavior. The title compound consists of l-alanine; an amino acid and maleic acid; an aromatic organic compound. It has been successfully synthesized and the single crystal has been grown by slow evaporation solution growth. The grown single crystal has been characterized by powder X-ray diffraction (PXRD) analysis and FTIR measurements. The crystalline perfection was examined by high-resolution X-ray diffraction (HRXRD) technique and found that the specimen quality is quite good. Optical behavior has been assessed by UV–Vis analysis and found that there is no absorption in the entire visible region. The relative second harmonic generation (SHG) efficiency measurement reveals that the incorporation of maleic acid to l-alanine leads to increase its value of SHG. The mechanical behavior and the thermal analysis have been carried out using Vickers microhardness and TG/DTA measurements respectively. Its hyperpolarizability was estimated by density functional theory (DFT).     

Half‐sandwich Ru (II) complexes containing (N,O) Schiff base ligands: Catalysts for base‐free transfer hydrogenation of ketones

Two new half‐sandwich Ru (II)(p‐cymene) complexes ( 1 and 2 ) containing dopamine‐based (N, O) Schiff base ligands ( L ¹ H and L ² H ) were synthesized and characterized by FT‐IR, UV–Visible and ¹H & ¹³C NMR spectral techniques, and elemental analyses. The spectroscopic and analytical data revealed monobasic bidentate coordination of the ligands with Ru ion. The molecular structures of L ¹ H , L ² H and 2 were further confirmed by single crystal X‐ray diffraction study. Complexes 1 and 2  have been employed as catalysts in the transfer hydrogenation of ketones using 2‐propanol as a hydrogen source at 85 °C under base‐free condition. Good to the excellent yield of secondary alcohols, gram scale synthesis, and high TON and TOF made this catalytic system interesting.     

Investigating the effect of π-configurations and methoxy substitution on donor and π- spacers based dyes for dye-sensitized solar cell applications–computational approach

Research on Chemical Intermediates - Triphenylamine and methoxy substituted triphenylamine-based dyes are examined by density-functional theory and time-dependent density-functional theory. The...     

Monomeric, tetrameric, and polymeric copper di-tert-butyl phosphate complexes containing pyridine ancillary ligands

The reaction of di-tert-butyl phosphate (((t)BuO)(2)P(O)(OH), dtbp-H) with copper acetate in the presence of pyridine (py) and 2,4,6-trimethylpyridine (collidine) has been investigated. Copper acetate reacts with dtbp-H in a reaction medium containing pyridine, DMSO, THF, and CH(3)OH to yield a one-dimensional polymeric complex [Cu(dtbp)(2)(py)(2)(mu-OH(2))](n) (1) as blue hollow crystalline tubes. The copper atoms in 1 are octahedral and are surrounded by two terminal phosphate ligands, two pyridine molecules, and two bridging water molecules. The mu-OH(2) ligands that are present along the elongated Jahn-Teller axis are responsible for the formation of the one-dimensional polymeric structure. Recrystallization of 1 in a DMSO/THF/CH(3)OH mixture results in the reorganization of the polymer and its conversion to a more stable tetranuclear copper cluster [Cu(4)(mu(3)-OH)(2)(dtbp)(6)(py)(2)] (2) in about 60% yield. The molecular structure of 2 is made up of a tetranuclear core [Cu(4)(mu(3)-OH)(2)] which is surrounded by six bidentate bridging dtbp ligands. While two of the copper atoms are pentacoordinate with a tbp geometry, the other two copper atoms exhibit a pseudooctahedral geometry with five normal Cu-O bonds and an elongated Cu-O linkage. The pentacoordinate copper centers bear an axial pyridine ligand. The short Cu.Cu nonbonded distances in the tetranuclear core of 2 lead to magnetic ordering at low temperature with an antiferromagnetic coupling at approximately 20 K (J(P) = -44 cm(-1), J(c) = -66 cm(-1), g = 2.25, and rho = 0.8%). When the reaction between di-tert-butyl phosphate (dtbp-H) and copper acetate was carried out in the presence of collidine, large dark-blue crystals of monomeric copper complex [Cu(dtbp)(2)(collidine)(2)] (3) formed as the only product. A single-crystal X-ray diffraction study of 3 reveals a slightly distorted square-planar geometry around the copper atom. Thermogravimetric analysis of 1-3 revealed a facile decomposition of the coordinated ligands and dtbp to produce a copper phosphate material around 500 degrees C. An independent solid-state thermolysis of all the three complexes in bulk at 500-510 degrees C for 2 days produced copper pyrophosphate Cu(2)P(2)O(7) along with small quantities of Cu(PO(3))(2) as revealed by DR-UV spectroscopic and PXRD studies.     

Vibrational spectra and structure of 5,6-diamino uracil and 5,6-dihydro-5-methyl uracil by density functional theory calculations

The molecular vibrations of 5,6-diamino uracil and 5,6-dihydro-5-methyl uracil were investigated in polycrystalline sample, at room temperature, by FT-IR and FT-Raman spectroscopies. The spectra were interpreted with the aid of normal coordinate analysis following a full structure optimization and force field calculations based on the density functional theory (DFT) using standard B3LYP/6-31G* and B3LYP/6-311+G** methods and basis set combinations. The DFT force field transformed to natural internal coordinates was corrected by a well-established set of scale factors that were found to be transferable to the title compounds. The infrared and Raman spectra were also predicted from the calculated intensities. Comparison of the simulated spectra with the experimental spectra provides important information about the ability of the computational method to describe the vibrational modes.     

Nickel(II) complexes of tripodal 4N ligands as catalysts for alkane oxidation using m-CPBA as oxidant: ligand stereoelectronic effects on catalysis

Several mononuclear Ni(II) complexes of the type [Ni(L)(CH(3)CN)(2)](BPh(4))(2) 1-7, where L is a tetradentate tripodal 4N ligand such as N,N-dimethyl-N',N'-bis(pyrid-2-ylmethyl)ethane-1,2-diamine (L1), N,N-diethyl-N',N'-bis(pyrid-2-ylmethyl)ethane-1,2-diamine (L2), N,N-dimethyl-N'-(1-methyl-1H-imidazol-2-ylmethyl)-N'-(pyrid-2-ylmethyl)ethane-1,2-diamine (L3), N,N-dimethyl-N',N'-bis(1-methyl-1H-imidazol-2-ylmethyl)ethane-1,2-diamine (L4), N,N-dimethyl-N',N'-bis(quinolin-2-ylmethyl)ethane-1,2-diamine (L5), tris(benzimidazol-2-ylmethyl)amine (L6) and tris(pyrid-2-ylmethyl)amine (L7), have been isolated and characterized using CHN analysis, UV-Visible spectroscopy and mass spectrometry. The single-crystal X-ray structures of the complexes [Ni(L1)(CH(3)CN)(H(2)O)](ClO(4))(2) 1a, [Ni(L2)(CH(3)CN)(2)](BPh(4))(2) 2, [Ni(L3)(CH(3)CN)(2)](BPh(4))(2) 3 and [Ni(L4)(CH(3)CN)(2)](BPh(4))(2) 4 have been determined. All these complexes possess a distorted octahedral coordination geometry in which Ni(II) is coordinated to four nitrogen atoms of the tetradentate ligands and two CH(3)CN (2, 3, 4) or one H(2)O and one CH(3)CN (1a) are located in cis positions. The Ni-N(py) bond distances (2.054(2)-2.078(3) ?) in 1a, 2 and 3 are shorter than the Ni-N(amine) bonds (2.127(2)-2.196(3) ?) because of sp(2) and sp(3) hybridizations of the pyridyl and tertiary amine nitrogens respectively. In 3 the Ni-N(im) bond (2.040(5) ?) is shorter than the Ni-N(py) bond (2.074(4) ?) due to the stronger coordination of imidazole compared with the pyridine donor. In dichloromethane/acetonitrile solvent mixture, all the Ni(ii) complexes possess an octahedral coordination geometry, as revealed by the characteristic ligand field bands in the visible region. They efficiently catalyze the hydroxylation of alkanes when m-CPBA is used as oxidant with turnover number (TON) in the range of 340-620 and good alcohol selectivity for cyclohexane (A/K, 5-9). By replacing one of the pyridyl donors in TPA by a weakly coordinating -NMe(2) or -NEt(2) donor nitrogen atom the catalytic activity decreases slightly with no change in the selectivity. In contrast, upon replacing the pyridyl nitrogen donor by the strongly σ-bonding imidazolyl or sterically demanding quinolyl/benzimidazolyl nitrogen donor, both the catalytic activity and selectivity decrease, possibly due to destabilization of the intermediate [(4N)(CH(3)CN)Ni-O˙](+) radical species. Adamantane is selectively (3°/2°, 12-17) oxidized to 1-adamantanol, 2-adamantanol and 2-adamantanone while cumene is selectively oxidized to 2-phenyl-2-propanol. In contrast to cyclohexane oxidation, the incorporation of sterically hindering quinolyl/benzimidazolyl donors around Ni(ii) leads to a high 3°/2° bond selectivity for adamantane oxidation. A linear correlation between the metal-ligand covalency parameter (β) and the turnover number has been observed.