Doping Transition Metal (Mn or Cu) Ions in Semiconductor Nanocrystals

Following growth doping strategy and using dopant oxides nanocrystals as dopant sources, we report here two different transition-metal ions doped in a variety of group II-VI semiconductor nanocrystals. Using manganese oxide and copper oxide nanocrystals as corresponding dopant sources, intense photoluminescence emission over a wide range of wavelength has been observed for different host nanocrystals. Interestingly, this single doping strategy is successful in providing such highly emissive nanocrystals considered here, in contrast with the literature reports that would suggest synthesis strategies to be highly specific to the particular dopant, host, or both. We investigate and discuss the possible mechanism of the doping process, supporting the migration of dopant ions from dopant oxide nanocrystals to host nanocrystals as the most likely scenario.

Electrophilic Substitution Reactions of Copper(II) Acetylacetoneimine Complexes with Arene Diazonium Ions

Copper(II) complexes of ethylene/propylene-bis(acetylacetoneimine), Cu(baen) or Cu(bapn), react quickly and quantitatively in aqueous methanol at the methine position with arene diazonium ions in a stepwise manner to yield mono- and di-substituted copper(II) complexes. All the complexes are paramagnetic with μeff∼1.88 B.M. In all the complexes the diazo substituted part of the ligand coordinates to the metal through the agr-nitrogen of the azo group and the imine nitrogen, forming glyoxaliminearylhydrazone type of ligand system. The complexes have been characterized by elemental analysis, electronic, esr, ir and mass spectroscopic methods.

Three different co-ordination geometries in the pentacopper(II) unit of [Cu5(OH)2(H2O)(O2CMe)6(Him)4][ClO4]2(Him = imidazole)

The reaction of imidazole (Him) with [Cu2(µ-O2CMe)4(H2O)2] in water–NaClO4 led to the formation of a polynuclear copper(II) complex, [Cu5(OH)2(H2O)(O2CMe)6(Him)4][ClO4]21, in which the pentanuclear units, showing four, five and six co-ordination geometries for the copper(II) centres and Cu Cu distances of 3.043(1), 3.178(1) and 3.578(1)Å, were linked by aqua bridges to give an intra-chain inter-unit Cu Cu separation of 4.507(1)Å.

Crystal structures, spectral and magnetic properties of (µ-hydroxo)(µ-acetato)dicopper(II) complexes containing chelating amines

The reaction of [Cu2(O2CMe)4(H2O)2] with N, N, N′, N′-tetramethylethane- 1,2-diamine (tmen) in ethanol yielded the dicopper(II) complex [Cu2(OH)(O2CMe)(tmen)2][ClO4]21. A similar reaction with N, N- dimethylethane- 1,2-diamine (dmen) afforded a crystalline product 2 in which two dicopper(II) complexes, [Cu2(OH)(O2CMe)(dmen)2][ClO4]22a and [Cu2(OH)(O2CMe)(H2O)2(dmen)2][ClO4]22b, are cocrystallized in a 1 : 1 molar ratio along with 2NaClO4. The crystal structures of 1 and 2 have been determined. The complexes have an asymmetrically dibridged [Cu2(µ-OH)(µ-O2CMe)]2+ core. The co-ordination geometry of the metal is square planar (CuO2N2). The copper atoms in 2b have a square-pyramidal CuO3N2 co-ordination sphere. The Cu Cu distances and Cu–O–Cu angles in 1, 2a and 2b are 3.339(2), 3.368(3), 3.395(7)Å, 120.1(2), 116.4(1) and 123.6(2)°, respectively. Complex 1 exhibits an axial ESR spectrum in a methanol glass giving g∥= 2.26 (A∥= 164 × 10–4 cm–1) and g⊥= 2.04. The ESR spectra obtained from the bulk material of the dmen product are indicative of the presence of two dimers, viz. complex 2a(g∥= 2.25, A∥= 165 × 10–4 cm–1; g⊥= 2.03) and 2b(g∥= 2.19, A∥= 184 × 10–4 cm–1; g⊥= 2.0). Variable-temperature magnetic susceptibility measurements on these complexes show an intramolecular antiferromagnetic coupling in the dimeric core. The fitting parameters are J=–27.8 cm–1, g= 2.1 for complex 1 and J=–10.1 cm–1, g= 2.0 for 2. The magnetostructural properties of the complexes are discussed. There is a linear correlation of the –2J values with the Cu Cu distances among dibridged complexes having square-planar copper(II) centres.

High-Throughput Study of the Cu(CH3COO)(2)center dot H2O-5-Nitroisophthalic Acid Heterocyclic Ligand System: Synthesis, Structure, Magnetic, and Heterogeneous Catalytic Studies of Three Copper Nitroisophthalates

A high-throughput screening was employed to identify new compounds in Cu(CH3COO)(2)center dot H2O-NIPA-heterocyclic ligand systems. Of the compounds identified, three compounds, Cu-3{(NO2)-C6H3-(COO)(2)}(3)(C3N6H6)] (1), Cu-2(mu(3)-OH)(H2O){(NO2)-C6H3-(COO)(2)}(CN4H)]center dot-(H2O) (II), and Cu-2(mu(3)-OH)(H2O){(NO2)-C6H3-(COO)(2}-)(CN5H2)]center dot 2(H2O) (III), have been isolated as good quality single crystals by employing conventional hydrothermal methods. Three other compounds, Cu-2{(NO2)-C6H3-(COO)(2)}-(CN4H)(H2O) (IIa), Cu-2{(NO2)-C6H3-(COO)(2)}(CN5H2) (IIIa), and Cu-2{(NO2)-C6H3-(COO)(2)}{(CN5H2)(2)}2H(2)O (IIIb), were identified by a combination of elemental analysis, thermogravimetric analysis (TGA), and IR spectroscopic studies, although their structures are yet to be determined. The single crystalline compounds were also characterized by elemental analysis, TGA, IR, UV vis, magnetic, and catalytic studies. The structures of the compounds have paddle wheel (I) and infinite Cu 0(H) Cu chains (II and HI) connected with NLPA and heterocyclic ligands forming two-(II) and three-dimensional (I and III) structures. The bound and lattice water molecules in 11 and 111 could be reversibly removed/inserted without affecting the structure. In the case of II, the removal of water gives rise to a structural transition, but the dehydrated phase reverts back to the original phase on prolonged exposure to atmospheric conditions. Magnetic studies indicate an overall antiferromagnetism in all of the compounds. Lewis acid catalytic studies indicate that compounds II and HI are active for cyanosilylation of imines.

Low-temperature structure of two copper-based precursors for MOCVD: Aquabis(tert-butyl acetoacetato)copper(II) and Bis(dipivaloylmethanido)copper(II)

The Cu atoms in aquabis(tert-butyl acetoacetato)copper(II),[Cu(C8H13O3)(2)(H2O)], and bis(dipivaloylmethanido)copper(II), [Cu(C11H19O2)(2)], adopt square-pyramidal and planar conformations, respectively, with average Cu--O distances of 1.933 Angstrom in the former (not including the water ligand) and 1.892 Angstrom in the latter. It is interesting to note that the lability of the tert-butyl and methyl groups in both structures, which renders even the location of the terminal C atoms difficult, is reduced at T = 130 K, enabling location of all the protons in the difference Fourier map.

Organic Additive-Mediated Synthesis of Novel Cobalt(II) Hydroxides

Electrochemical precipitation of cobalt(II) hydroxide from nitrate solutions containing organic molecules, such as glucose, fructose, lactose, glycerol, and citric acid, yields a new modification of cobalt (II) hydroxide (a = 3.09 +/- 0.03 Angstrom, c = 23.34 +/- 0.36 Angstrom) that is isostructural with cu-nickel hydroxide; precipitation in the absence of organic additives gives the stable, brucite-like, beta-CO (OH)(2). (C) 1995 Academic Press, Inc.

Unusual ribose conformation in a ternary copper(II) 2?deoxyribonucleotide complex

The ternary metal deoxyribonucleotide complex [Cu(bzim)(5?-dGMP)(H2O)3](bzim = benzimidazole, 5?-dGMP = 2?-deoxyguanosine 5?-monophosphate) has been prepared and the structure analysed by X-ray diffraction. The compound crystallizes in the space group P1 with a= 7.069(6), b= 13.959(10), c= 14.204(12)Å, ?= 75.12(6), ?= 94.15(6), ?= 97.98(6)° and Z= 2. The structure was solved by the heavy-atom method and refined by full-matrix least-squares procedures on the basis of 2813 observed [I[gt-or-equal] 3?(I)] reflections to final R and R? values of 0.050 and 0.052 respectively. There are two independent molecules in the asymmetric unit and both copper(II) centres have square-pyramidal co-ordination geometry. An unusual feature of the structure is the co-ordination of the metal by N(7) of the base, in the presence of a ?-aromatic amine, bzim. The structure is stabilized by intermolecular base�bzim stacking. The nucleotides of both the molecules have an anti conformation about the glycosyl bond, and a gauche-gauche conformation about the C(4?)�C(5?) bond. A feature of particular interest is the unusual sugar conformation. The base furanose rings of the two nucleotide molecules adopt C(3?)-exo/C(2?)-endo pucker and C(3?)-exo pucker respectively.

Magneto-structural correlation in (mu-alkoxo/hydroxo)(mu-carboxylato)dicopper(II) systems: Synthesis, X-ray structure and magnetic properties of aquo(mu-hydroxo) (mu-arylcarboxylato)bis(N,N,N ',N '-tetramethylethane-1,2-diamine)dicopper(II) diperchlorate

Asymmetrically dibridged dicopper(II) complexes, [Cu-2(OH)(O2CC6H4-p-Me)(tmen)(2)(H2O)](ClO4)(2) (1) and [Cu-2(OH)(O2CC6H4-p-OMe)(tmen)(2)(H2O)](ClO4)(2) (2) (tmen = N,N,N',N'-tetramethylethane-1,2-diamine), were prepared and structurally characterized. Complex 1 crystallizes in the monoclinic space group P2(1)/a with a = 17.718(2), b = 9.869(1), c = 19.677(2) Angstrom, beta = 115.16(1)degrees, V = 3114.3(6) Angstrom(3) and Z = 4. The structure was refined to R(wR(2)) = 0.067(0.178). Complex 2 crystallizes in the monoclinic space group P2(1)/a with a = 17.695(3), b = 9.574(4), c = 20.104(2) Angstrom, beta = 114.18(1)degrees, V = 3107(1) Angstrom(3) and Z = 4. The final residuals are R(wR(2)) = 0.067(0.182). The complexes have a [Cu-2(mu-OH)(mu-OH)(mu-O2CAr)](2+) core with tmen Ligands occupying the terminal sites of the core. In addition, one copper is axially bound to a water molecule. The Cu ... Cu distances and the Cu-OH Cu angles in the core are 3.394(1) Angstrom, 124.4(2)degrees for 1 and 3.374(1) Angstrom, 123.3(3)degrees for 2. The complexes show axial X-band EPR spectral features in methanol glass at 77 K giving g(perpendicular to) = 2.02, g(parallel to) = 2.3 (A(parallel to) = 165 x 10(-4) cm(-1)) and a visible band near similar to 630 nm in methanol. The complexes are weakly antiferromagnetic. A theoretical fit of the magnetic susceptibility data in the temperature range 40-295 K gives -J = 10 cm(-1), g = 2.05 for 1 and -J = 10 cm(-1), g = 2.0 for 2. Plots of -2J versus the Cu-OH-Cu angle (phi) in this class of asymmetrically dibridged dicopper(II) complexes having d(x2-y2)-d(x2-y2) magnetic orbitals show a linear magneto-structural correlation: -2J(cm(-1)) = 11.48 phi(deg) - 1373.

Synthesis, crystal structure and magnetic properties of a polymeric copper(II) Schiff-base complex having binuclear units covalently linked by isonicotinate ligands

The polynuclear copper(II) complex [{Cu2L(O2CC5H4N)}. C2H5OH](x) (1), where H3L is a 1∶2 Schiff base derived from 1,3-diaminopropan-2-ol and salicylaldehyde, has been prepared and structurally characterized. The structure consists of a one-dimensional zigzag chain in which the binuclear [Cu2L](+) units are covalently linked by isonicotinate ligands to give a syndiotactic arrangement of the copper ions protruding outside the chain. In the basic unit, the copper(II) centres are bridged by an alkoxo and a carboxylato ligand, giving a Cu ... Cu distance of 3.492(3) Angstrom and a Cu-O-Cu angle of 130.9(2)degrees. While one copper centre has a square-planar geometry, the other copper is square-pyramidal with the pyridine nitrogen being the axial ligand. The visible electronic spectrum of 1 shows a broad d-d band at 615 nm. The complex shows a rhombic X-band EPR spectral pattern in the polycrystalline phase at 77 K. Magnetic susceptibility measurements in the temperature range 22 to 295 K demonstrate the antiferromagnetic behaviour of 1. A theoretical fit to the magnetic data is based on a model assuming 1 as an equimolar mixture of copper atoms belonging to an antiferromagnetically coupled one-dimensional Heisenberg chain with the other copper atoms outside the chain behaving like paramagnetic centres.

Self-assembled molecular films of tetraamino metal (Co, Cu, Fe) phthalocyanines on gold and silver. Electrochemical and spectroscopic characterization

The formation of molecular films of 2,9,16,23-tetraamino metal phthalocyanines [TAM(II)Pc; M (II) = Co, Cu, and TAM(III)Pc; M = Fe] by spontaneous adsorption on gold and silver surfaces is described. The properties of these films have been investigated by cyclic voltammetry, impedance, and FT-Raman spectroscopy. The charge associated with Co(II) and Co(I) redox couple in voltammetric data leads to a coverage of (0.35+/-0.05) x 10(-10) mol cm(-2), suggesting that the tetraamino cobalt phthalocyanine is adsorbed as a monolayer with an almost complete coverage. The blocking behavior of the films toward oxygen and Fe(CN)(6)(3-/4-) redox couple have been followed by cyclic voltammetry and impedance measurements. This leads to an estimate of the coverage of about 85 % in the case of copper and the iron analogs. FT-Raman studies show characteristic bands around 236 cm(-1) revealing the interaction between the metal substrate and the nitrogen of the -NH2 group on the phthalocyanine molecules.

Texture evolution in an Al-Cu alloy during equal channel angular pressing: the effect of starting microstructure

In this article, the effect of initial microstructure on the texture evolution in 2014 Al alloy during equal channel angular pressing (ECAP) through route A has been reported. Three heat treatment conditions were chosen to generate the initial microstructures, namely (i) the recrystallization anneal (as-received), (ii) solution treatment at 768 K for 1 h, and (iii) solution treatment (768 K for 1 h) plus aging at 468 K for 5 h. Texture analyses were performed using orientation distribution function (ODF) method. The texture strength after ECAP processing was different for the three samples in the order, solutionised > solutionised plus aged condition > as-received. The prominent texture components were A (E) /(A) over bar (E) and B(E)/(B) over bar (E) in addition to several weaker components for the three materials. The strong texture evolution in solutionised condition has been attributed to higher strain hardening of the matrix due to higher amount of solute. In case of the as-received as well as solutionised plus aged alloy, the weaker texture could be due to the strain scattering from extensive precipitate fragmentation and dissolution during ECAP.

Dicopper(II) complexes showing DNA hydrolase activity and monomeric adduct formation with bis(4-nitrophenyl)phosphate

Ferromagnetic dicopper(II) complexes [Cu(2)(mu-O(2)CCH(3))(mu-OH)(L)(2)(mu-L(1))](PF(6))(2), where L = 1,10-phenanthroline (phen), L(1) = H(2)O in 1 and L = dipyrido[3,2-d:2',3'-f]quinoxaline (dpq), L(1) = CH(3)CN in 2, are prepared and structurally characterized. Crystals of 1 and 2 belong to the monoclinic space group of P2(1)/n and P2(1)/m, respectively. The copper(II) centers display distorted square-pyramidal geometry having a phenanthroline base and two oxygen atoms of the bridging hydroxo and acetate group in the basal plane. The fifth coordination site has weak axially bound bridging solvent molecule H(2)O in 1 and CH(3)CN in 2. The Cu center dot center dot center dot Cu distances are 3.034 and 3.046 angstrom in 1 and 2, respectively. The complexes show efficient hydrolytic cleavage of supercoiled pUC19 DNA as evidenced from the mechanistic studies that include T4 DNA ligase experiments. The binuclear complexes form monomeric copper(II) adducts [Cu(L)(2)(BNPP)](PF(6)) (L = phen, 3; dpq, 4) with bis(4-nitrophenyl)phosphate (BNPP) as a model phosphodiester. The crystal structures of 3 and 4 reveal distorted trigonal bipyramidal geometry in which BNPP binds through the oxygen atom of the phosphate. The kinetic data of the DNA cleavage reactions of the binuclear complexes under pseudo- and true-Michaelis-Menten conditions indicate remarkable enhancement in the DNA hydrolysis rate in comparison to the control data. (C) 2011 Elsevier B.V. All rights reserved.

Oxidative DNA cleavage, cytotoxicity and antimicrobial studies of L-ornithine copper (II) complexes

New ternary copper (II) complexes, Cu(L-orn)(B)(Cl)](Cl center dot 2H(2)O) (1-2) where L-orn is L-ornithine, B is an N,N-donor heterocyclic base, viz. 2,2'-bipyridine (bpy, 1) and 1,10-phenanthroline (phen, 2), were synthesized and characterized by various spectroscopic techniques. Complex 2 is characterized by the X-ray single crystallographic method. The complex shows a distorted square-pyramidal (4 + 1) CuN3OCl coordination sphere. Binding interactions of the complexes with calf thymus DNA (CT-DNA) were investigated by UV-Vis absorption titration, ethidium bromide displacement assay, viscometric titration experiment and DNA melting studies. Complex 2 shows appreciable chemical nuclease activity in the presence of 3-mercaptopropionic acid (MPA). The complexes were subjected to in vitro cytotoxicity studies against carcinomic human alveolar basal epithelial cells (A-549) and human epithelial (HEp-2) cells. The IC50 values of 1 and 2 are less than that of cisplatin against HEp-2 cell lines. MIC values for 1 against the bacterial strains Streptococcus mutans and Pseudomonas aeruginosa are 0.5 mM. (C) 2012 Elsevier Ltd. All rights reserved.

DNA Binding and Oxidative Cleavage Activity of Ternary (alpha-Lipoic Acid) Copper(II) Complex of Heterocyclic Base

Ternary copper(II) complex Cu(a-lipo)(phen)(Cl)](NO3) where a-lipo = a-lipoic acid, phen is N, N-donor heterocyclic base, 1,10-phenanthroline was synthesized, characterized, and its DNA binding and cleavage activity were studied. Binding interactions of the complex with calf thymus (CT) DNA has been investigated by emission, viscosity, and DNA melting studies. The complex shows efficient oxidative cleavage of SC-DNA in the presence of 3-mercaptopropionic acid involving hydroxyl radical species, and results of control experiments exhibit the inhibition of DNA cleavage in the presence of hydroxyl radical scavengers, viz. DMSO and KI.