New symmetrical dinucleating ligand based assembly of bridged dicopper(II) and dizinc(II) centers: Synthesis, structure, spectroscopy, magnetic properties and glycoside hydrolysis

Two dinuclear copper(II) complexes Li(H2O)(3)(CH3OH)](4)Cu2Br4]Cu-2(cpdp)(mu-O2CCH3)](4)(OH)(2) (1), Cu (H2O)(4)]Cu-2(cpdp)(mu-O2CC6H5)](2)Cl-2 center dot 5H(2)O (2), and a dinuclear zinc(II) complex Zn-2(cpdp)(mu-O2CCH3)] (3) have been synthesized using pyridine and benzoate functionality based new symmetrical dinucleating ligand, N, N'-Bis2-carboxybenzomethyl]-N, N'-Bis2-pyridylmethyl]-1,3-diaminopropan-2-ol (H(3)cpdp). Complexes 1, 2 and 3 have been synthesized by carrying out reaction of the ligand H3cpdp with stoichiometric amounts of Cu-2(O2CCH3)(4)(H2O)(2)], CuCl2 center dot 2H(2)O/C6H5COONa, and Zn(CH3COO)(2)center dot 2H(2)O, respectively, in methanol in the presence of NaOH at ambient temperature. Characterizations of the complexes have been done using various analytical techniques including single crystal X-ray structure determination. The X-ray crystal structure analyses reveal that the copper(II) ions in complexes 1 and 2 are in a distorted square pyramidal geometry with Cu-Cu separation of 3.455(8) angstrom and 3.492(1)angstrom, respectively. The DFT optimized structure of complex 3 indicates that two zinc(II) ions are in a distorted square pyramidal geometry with Zn-Zn separation of 3.492(8)angstrom. UV-Vis and mass spectrometric analyses of the complexes confirm their dimeric nature in solution. Furthermore, H-1 and C-13 NMR spectroscopic investigations authenticate the integrity of complex 3 in solution. Variable-temperature (2-300 K) magnetic susceptibility measurements show the presence of antiferromagnetic interactions between the copper centers, with J = -26.0 cm(-1) and -23.9 cm(-1) ((H) over cap = -2JS(1)S(2)) in complexes 1 and 2, respectively. In addition, glycosidase-like activity of the complexes has been investigated in aqueous solution at pH similar to 10.5 by UV-Vis spectrophotometric technique using p-nitrophenyl-alpha-D-glucopyranoside (4) and p-nitrophenyl-beta-D-glucopyranoside (5) as model substrates. (C) 2015 Elsevier B.V. All rights reserved.

Development of an automated ultrasonic spray pyrolysis system and the growth of Cu2ZnSnS4 thin films

An automated ultrasonic spray pyrolysis system is fabricated for the growth of thin films. The system is equipped with x-y movement and enables film deposition in different patterns and spray rates. Cu-2(Zn,Sn)S-4 (CZTS) films are deposited using this setup. The substrate temperature (T-s) is varied from 240 to 490 degrees C. Kesterite CZTS phase is observed in all the films together with binary phases. The films prepared at T-s <340 degrees C showed SnxSy phase and those at T-s >340 degrees C showed Cu2S phase. Sulfur incorporation is maximum (40%) at 440 degrees C and the films showed better morphology. The Cu and S concentrations are varied to remove binary phases. Depth wise elemental analysis confirmed the existence of single phase CZTS. p-Type CZTS films of resistivity in the range of 10(2)-10(3) Omega cm are obtained. (C) 2015 Elsevier B.V. All rights reserved.

Complexes Of Imidazoline-2-Thione And Its 1-Methyl Analogue With Cu(Ii), Zn(Ii), Cd(Ii) And Hg(Ii) Salts

The reaction of Cu(II), Zn(II), Cd(II) and Hg(II) chlorides and bromides with imidazoline-2-thione (IZT) and its N-methyl derivative (NMIZT) yields complexes of stoichiometry ML3X2 and ML2X (IZT) and its N-methyl derivative (NMIZT) yields complexes of stoichiometry ML3X2 and ML2X (where M=Cu(I)); copper(II) halides yield Cu(I) complexes. On the basis of infrared and 13C n.m.r.

Cu (DPM)2-initiated vinyl polymerization

The behavior of cupric dipivaloylmethide in vinyl polymerization systems was investigated with a view to understanding the mechanism of polymerization initiation. Results of polymerization reactions together with spectral investigation data are presented. Polymerization in the presence of the chelate proceeds through a free-radical process. The corresponding kinetic and transfer constants and activation energy values suggest a normal propagation step. With the help of spectral data an attempt is made to suggest a plausible mechanism of initiation.

2-Thioacetamido thiazole as an ambidentate ligand. Complexes of Zn(II), Cd(II), Hg(II) and Cu(I)

Metal complexes of thiazoles have been studied in recent years[I-3] because of their biochemical importance[4,5]. However, data on metal complexes of thiazole derivatives containing another coordinating function are limited[2]. We have synthesized and examined the donor characteristics of a new ligand, 2-thioacetamide thiazole (TATZ)(I) towards chlorides and bromides of Zn(II), Cd(II), Hg(II) and Cu(I). The presence of four potential donor atoms and extensive charge delocalization should render TATZ a versatile ligand.

Cu(II) complexes of 1-benzyl-2-phenyl-benzimidazole

Copper(II) complexes of 1-benzyl-2-phenylbenzimidazole (BPBI) of the general formula Cu(BPBI)2X2, nH2O [X= Cl-, Br-, NO3 or OAc- (n = O) and X = NO3- or 1 2SO42-(n = 2H2O)] have been prepared. The complexes are found to be nonelectrolytes in nitrobenzene. Conductivity in nonaqueous media, magnetic susceptibilities and i.r. and electronic spectra of the complexes are reported. A tetragonally distorted octahedral structure has been suggested for these complexes.

Crystal structure of copper ammonium oxalate dihydrate, Cu(NH 4)2(C2O4)2.2H 2O

The crystal structure of copper ammonium oxalate dihydrate (space group P1̃) has been derived from a refinement of the two-dimensional (hk0) and (0kl) x-ray data using the atomic coordinateis of the isomorphous salt CuK 2(C2O4)2.2H2O as the starting point of the analysis. In contrast to the chromium complexes of oxalic acid the C-C bonds in both the two nonequivalent oxalate ions in the unit cell are single bonds (1.58 and 1.61 Å) consistent with the conclusion of Jeffrey and Parry that the carboxyl groups of the oxalate ion are separated by a pure a bond with little or no π conjugation across the molecule. Both the oxalate ions are slightly nonplanar. The copper ions occupy the special positions (0, 0, 0) and 0, 1/2, 0) and their coordination is of the distorted octahedral type with four nearest oxygen neighbors ( ≃ 2 Å) at the corners of a square and two more distant atoms along the octahedral bond direction. The environment of the NH4+ ions consists of eight nearest oxygen atoms at a mean distance of 3 Å.

Structure of a monochloro bridged polymeric copper(II)-di-2-pyridylamine complex: [Cu(dipyam)Cl(NO3)].0.5H2O

Di-2-pyridylaminechloronitratocopper(II) hemihydrate, [CuCl(NO3)(C10H9N3)].0.5H2O, M(r) = 341.21, monoclinic, P2(1)/a, a = 7.382 (1), b = 21.494 (4), c = 8.032 (1) angstrom, beta = 94.26 (1)-degrees, V = 1270.9 angstrom 3, Z = 4, D(m) = 1.78, D(x) = 1.782 g cm-3, lambda(Mo K-alpha) = 0.7107 angstrom, mu(Mo K-alpha) = 19.47 cm-1, F(000) = 688. The structure was solved by the heavy-atom method and refined to a final R value of 0.034 for 2736 reflections collected at 294 K. The structure consists of polymeric [Cu(dipyam)Cl(NO3)] units bridged by a chloride ion.

A novel metal binding mode of a pyrimidine nucleotide. Crystal structure of [Cu(5′-UMP)(im)2(H2O)]·4H2O

X-ray analysis of the ternary complex [Cu(5′-UMP)(im)2(H2O)]·4H2O, where 5′-UMP uridine-5′-monophosphate and IM = imidazole, reveals a novel metal binding mode of pyrimidine nucleotide through the ribose group.

Synthesis and x-ray crystal structure of a CuII-theophylline complex: [Cu(theo)2 (H2O)3]·2H2O

The complex [Cu-II (theo)(2)(H2O)(3)].2H(2)O (theo = theophylline) was obtained from aqueous solution. The crystals belong to the monoclinic system, space group P2(1)/n, and are reflection twins about the (001) face. The structure was solved using data from a twinned crystal and refined to final R and R(W) values of 0.069 and 0.064, respectively. Copper has a square-pyramidal coordination with two thee molecules coordinating through N(7) at equatorial positions. The remaining sites are occupied by water molecules. O(6) of one of the thee molecules is at the other axial site at a longer distance of 3.18 Angstrom. This could lead to an alternate (4+1+1) octahedral coordination geometry for Cu-II. The packing is stabilized by stacking interactions between the theophylline moieties at an average separation of 3.46 Angstrom.

New La2CuO4 derivatives La(2-2x)Sr(2x)Cu(1-x)M(x)O(4) (M=Ti, Mn, Fe, or Ru): A study of linear Cu-O-M electronic interaction in two dimensions

Oxides of the general formula La2-2xSr2xCu1-xII,M(x)(IV)O(4) (M = Ti, Mn, Fe, or Ru), crystallizing in the tetragonal K,NIF, structure, have been synthesized. For M=Ti, only the x=0,5 member could be prepared, while for M=Mn and Fe, the composition range is 0<x<1.0, and for M=Ru, the composition range is 0<x less than or equal to 0.5. There is no evidence for an ordering of Cu(II) and M(IV) in the x = 0.5 members. While the members of the M=Ti, Mn, and Ru series are semiconducting/insulating, the members of the M=Fe series are metallic, showing a broad metal-semiconductor transition around 100 K for O<x less than or equal to 0.15 that is possibly related to a Cu(II)-O-Fe(IV) <--> Cu(III)-O-Fe(III) valence degeneracy. Increasing the strontium content at the expense of lanthanum in La2-2xSr2xCu1-xFexO4 for x less than or equal to 0.20 renders the samples metallic but not superconducting. (C) 1997 Academic Press.

Oxidation of aqueous sulphur dioxide catalysed by poly-4-vinylpyridine-Cu(II) complex .2. Combined homogeneous and heterogeneous phase oxidation

Aqueous phase oxidation of sulphur dioxide at low concentrations catalysed by a PVP-Cu complex in the solid phase and dissolved Cu(II) in the liquid phase is studied in a rotating catalyst basket reactor (RCBR). The equilibrium adsorption of Cu(II) and S(VI) on PVP particles is found to be of the Langmuir-type. The diffusional effects of S(IV) species in PVP-Cu resin are found to be insignificant whereas that of product S(VI) are found to be significant. The intraparticle diffusivity of S(VI) is obtained from independent tracer experiments. In the oxidation reaction HSO3- is the reactive species. Both the S(IV) species in the solution, namely SO2(aq) and HSO3- get adsorbed onto the active PVP-Cu sites of the catalyst, but only HSO3- undergoes oxidation. A kinetic mechanism is proposed based on this feature which shows that SO2(aq) has a deactivating effect on the catalyst. A rate model is developed for the three-phase reaction system incorporating these factors along with the effect of concentration of H2SO4 on the solubility of SO2 in the dilute aqueous solutions of Cu(II). Transient oxidation experiments are conducted at different conditions of concentration of SO2 and O-2 in the gas phase and catalyst concentration, and the rate parameters are estimated from the data. The observed and calculated profiles are in very good agreement. This confirms the deactivating effect of nonreactive SO2(aq) on the heterogeneous catalysis.

First-principles electronic structure of the delafossites ABO(2) (A=Cu, Ag, Au; B=Al, Ga, Sc, In, Y): evolution of d(10)-d(10) interactions

While bonding between d(10) atoms and ions in molecular systems has been well studied, less attention has been paid to interactions between such seemingly closed shell species in extended inorganic solids. In this contribution, we present visualizations of the electronic structures of the delafossites ABO(2) (A = Cu, Ag, Au) with particular emphasis on the nature of d(10)-d(10) interactions in the close packed plane of the coinage metal ion. We find that on going from Cu to Ag to Au, the extent of bonding between A and A increases. However, the structures (in terms of distances) of these compounds are largely determined by the strongly ionic 13,11 0 interaction and for the larger B ions Sc, In and Y, the A atoms are sufficiently well-separated that A-A bonding is almost negligible. We also analyze some interesting differences between Ag and Au, including the larger A-O covalency of the Au. The trends in electronic structure suggest that the Ag and Au compounds are not good candidate transparent conducting oxides. (C) 2002 Editions scientifiques et medicales Elsevier SAS. All rights reserved.

Synthesis and DNA binding studies of Ni(II), Co(II), Cu(II) and Zn(II) metal complexes of N(1),N(5)-bis[pyridine-2-methylene]-thiocarbohydrazone Schiff-base ligand

The thiocarbohydrazone Schiff-base ligand with a nitrogen and sulphur donor was synthesized through condensation of pyridine-2-carbaldehyde and thiocarbohydrazide. Schiff-base ligands have the ability to conjugate with metal salts. A series of metal complexes with a general formula [MCl(2)(H(2)L)]center dot nH(2)O (M=Ni, Co, Cu and Zn) were synthesized by forming complexes of the N(1),N5-bis[pyridine-2-methylene]thiocarbohydrazone (H2L) Schiff-base ligand. These metal complexes and ligand were characterized by using ultraviolet-visible (UV-Vis), Fourier Transform Infrared (FT-IR), (1)H and (13)C NMR spectroscopy and mass spectroscopy, physicochemical characterization, CHNS and conductivity. The biological activity of the synthesized ligand was investigated by using Escherichia coli DNA as target. The DNA interaction of the synthesized ligand and complexes on E. coli plasmid DNA was investigated in the aqueous medium by UV-Vis spectroscopy and the binding constant (K(b)) was calculated. The DNA binding studies showed that the metal complexes had an improved interaction due to trans-geometrical isomers of the complexes than ligand isomers in cis-positions. (C) 2011 Elsevier B.V. All rights reserved.

Solubilities of Pb+2, Bi+3, Sb+3 and Cu+1 sulphides in (NaCl KCl Na2S) melts

Solubilities of common metal sulfides have been determined in the (NaCl+KCl) eutectic melt with and without Na2S. A novel gas-phase equilibrium technique has been used for PbS, Bi2S3, and So2S3, and an improved liquid phase equilibrium technique for Cu2S, which eliminates the errors due to physical entrapment of the sulfide phase and segregation on quenching, enabling precise measurements to be made. Solubilities in the (NaCl+KCl) eutectic melt were determined as a function of temperature in the rante 700° to 950°C, and were found to be small. The partial molar heats of mixing of the sulfides in the eutectic melt have been calculated from the solubility measurements, to be 13.3, 31.4, 37.1, and 49.0 kcal for PbSs), Sb2S2(l), and Cu2S(s), respectively. Sodium sulfide addition was observed to enhance these solubilities, the effect being largest for Cu2S followed by Sb2S3, Bi2S3, and PbS. This effect is explained qualitatively. It was observed that PbS and Sb2S3 obey Henry's law up to saturation in (NaCl+KCl+Na2S) melts.