The role of methyl and benzyl substituted dithiocarbazate of 2-acetyl pyridine for the formation of bridged dimeric and unbridged monomeric copper(II) complexes and catecholase mimetic activity of the complexes

Monomeric [Cu(L1)Cl] (1) and dimeric [Cu(L2)Cl]2 (2) copper(II) complexes, where HL1 = methyl-2-(1-(pyridine-2-yl)ethylidene)-hydrazine-1-carbodithioate and HL2 = benzyl-2-(1-(pyridine-2-yl)ethylidene)hydrazine-1-carbodithioate, have been synthesized and characterized by X-ray crystallography, TGA and spectral methods. Complex 1 crystallizes in a space group P21/n and adopts a square planar environment surrounding the Cu ion, and complex 2 is a triclinic crystal system with space group Pī. Complex 2 is a centrosymmetric dimer where each copper atom forms two chloro bridges and completes five coordination with the tridentate NNS donor. Density functional calculations demonstrate that chloro-unbridged structure of 1 is favored by London dispersion between its layers. It is noticed that the layers are usually packed closely in the solid phase, such attractive interactions are sterically hindered between the layers of 2. Due to the presence of large phenyl group that extend from one layer to the other, the layers cannot slide on top of each other. This leads to the chloro-bridged structure of 2 stabilized by electrostatic interactions between Cu and Cl atoms located at different layers. Both complexes exhibit prominent catecholase activity in methanol following the oxidation of 3,5-di-tert-butyl catechol (DTBC) to the corresponding quinone. Based on the observed turn over frequency of 1 (25.19 h−1) and 2 (10.76 h−1), the monomeric complex demonstrates more catechol mimetic oxidation than the dimer. A plausible mechanism of catecholase activity has been discussed.publishe

An unusual iminoacylation of 2-amino pyridyl thiazole: Synthesis, X-ray crystallography and DFT study of copper(II) amidine complexes and their cytotoxicity, DNA binding and cleavage study

Insertion of acetonitrile in the exocyclic NH2 group of the thiazole unit of 2-amino-4-(2-pyridyl)thiazole (HL) in the presence of copper chloride results in the formation of the monomeric amidine complex [Cu{LC(Me)double bondNH)}Cl2] (1). The same reaction of HL and copper(II) perchlorate yields the complex [Cu(HL)2](ClO4)2 (2), without acetonitrile insertion. However, the presence of a spacer donor, e.g. pyrazine, in the reaction medium results in the formation of a dinuclear amidine derivative, [(ClO4){LC(Me)double bondNH}Cu(μ-pyrazine)Cu{LC(Me)double bondNH}(ClO4)] (ClO4)2 (3). Complexes 1 and 3 are the first examples of copper assisted iminoacylation of 2-amino pyridylthiazole derivatives, confirming a nitrile to amidine transformation. The new complexes were characterized by single crystal X-ray crystallography, cyclic voltammetry and a DFT study. The complexes have a potential cytotoxic effect in human monocytic cells (U937) with IC50 values ranging from 0.84 to 4.5 μM. Significant necrotic activities are ascertained by a lactate dehydrogenase (LDH) enzyme release assay. The interaction with calf thymus (CT) DNA shows the binding constant (Kb) values are ∼104 M−1. The chemical nuclease activity of 1, 2 and 3 result in 65, 99 and 80% relaxation of supercoiled DNA at 10 μM in the presence of glutathione (GSH, 1 mM), respectively. The study with radical scavengers proved that a hydroxyl or singlet oxygen-like species is responsible for the DNA degradation.publishe

Synthesis, characterization, cytotoxicity effect and DNA cleavage study of symmetric dinuclear chloro and azido bridged copper(II) complexes of napthyl-pyrazole based ligand

Symmetric dinuclear chloro copper(II) complex [Cu(L)(Cl)(µ-Cl)]2 (1) and azo dinuclear azido copper(II) complex [Cu2(L)2(N3)3(µ2-N3)]n (2) [where L represents (5-methyl-pyrazol-1-ylmethyl)-napthalen-1-ylmethyl-amine] have been synthesized to examine the effect of napthyl group in the structure of pyrazole based dinuclear copper(II) complexes in DNA nuclease activity. The structure of 1 and 2 are characterized by X-ray crystallography, electrochemistry and various spectroscopic techniques. Coordinating ligand L is generated in situ from bis(3,5-dimethyl-pyrazol-1-ylmethyl)-napthalen-1-ylmethyl-amine (A) during complexation. Cytotoxic potential of free ligand (A), synthesized complexes 1, 2 and one cobalt(II) complex derived from ligand A, CoII(A)Cl2 (3) are analyzed using MTT cytotoxicity assay in U937 human monocytic cell line. Complexes 1 and 2 show very potent cytotoxicity (IC50 = 13–17 μM); the best IC50 value is found for 1. LDH assay revealed that A and 3 has greater necrotic activity than the copper complexes. However, the results of DNA cleavage study clearly demonstrated that symmetric bridged dinuclear complexes with napthyl group lead to high level of nuclease activity 72–75% in the presence of glutathione. The bridged dinuclear copper(II) complexes undergo facile transformation to Cu(I) centre through inner sphere electron transfer mechanism (ISET) in presence of glutathione which facilitate the formation of free radicals/ions for DNA cleavage. Lacking of any reducible metal center in mononuclear cobalt(II) complex make it inactive towards free radicals generation in DNA cleavage activity.publishe

Facile synthesis of nanocrystalline wurtzite Cu-In-S by amine-assisted decomposition of precursors

Phase-pure ternary wurtzite Cu-In-S nanocrystals have been synthesized by a simple amine-assisted decomposition of mixed precursor complexes derived from S-methyl dithiocarbazate (SMDTC) at a relatively low temperature without using any external surfactant. The crystal phase, morphology, crystal lattice, and chemical composition of the as-prepared products were analyzed by using X-ray diffraction, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and energy-dispersive X-ray spectroscopy (EDX). The optical properties show the pronounced quantum confinement effect in nanocrystals. A possible growth mechanism has been suggested for the formation of anisotropic wurtzite Cu-In-S It is believed that a combined effect of the chelating amine and precursors containing CH(3)S unit plays a key role in the formation of the metastable phase of wurtzite Cu-In-S. (C) 2010 Elsevier Inc. All rights reservedclose1

Nanocrystalline copper sulfide of varying morphologies and stoichiometries in a low temperature solvothermal process using a new single-source molecular precursor

Surfactantless synthesis of copper sulfide nanoparticles (NPs) with varied morphologies such as hexagonal rods, rhombohedral, and spherical, has been carried out via low-temperature thermolysis of a new single-source precursor, [Cu(SMDTC)Cl-2], (where SMDTC is S-methyl dithiocarbazate). The reaction parameters e.g., temperature and nature of solvent can be used to control the size and morphology of the nanoparticles. It is observed that the solvents played an important role to control the morphology and stoichiometry of copper sulfide. The anisotropic absorption by the chelating solvent (diamine or ethyleneglycol) at the different facets of the newborn microcrystals results the growth of one-dimensional (ID) copper sulfide NPs. The possible formation mechanism of copper sulfide NPs has also been discussed. (C) 2012 Elsevier Masson SAS. All rights reservedclose

High-yield synthesis of quantum-confined CdS nanorods using a new dimeric cadmium(II) complex of S-benzyldithiocarbazate as single-source molecular precursor

A convenient solvothermal single-source route has been developed for the bulk synthesis of CdS nanorods using new air stable dimeric cadmium(II) complex of S-benzyldithiocarbazate, [Cd(PhCH(2)SC(=S)NHNH(2))Cl(2)](2), at a relatively low temperature. The decomposition of the precursor was made by heating at 160 degrees C in hexamethylenediamine (HMDA) to give amine capped CdS nanocrystals having yield ca. 90%; nano-dimensional rods are clearly visible in transmission electron microscope (TEM). The nanorods have been further characterized by X-ray diffraction (XRD), energy dispersed X-ray spectroscopy (EDX), FTIR and optical measurements. The structure of precursor was also established by single crystal X-ray crystallography. (C) 2009 Elsevier Masson SAS. All rights reservedclose2

Synthesis, spectroscopy and thermal behavior of new lead(II) complexes derived from S-methyl/benzyldithiocarbazates (SMDTC/SBDTC): X-ray crystal structure of [Pb(SMDTC)(NO3)(2)]

Lead(II) complexes of S-methyldithiocarbazate (SMDTC), [Pb(SMDTC)(NO3)(2)] (1) and S-benzyldithiocarbazate (SBDTC), [Pb(SBDTC)(NO3)(2)] (2) have been synthesized for the. rst time and characterized by elemental analysis, IR and TGA techniques. The complexes were obtained by addition of the appropriate ligand to an aqueous ethanolic solution of lead(II) nitrate in 1:1 molar ratio. The X-ray crystal structure of complex 1 has been determined by single crystal X-ray diffractometry. In complex 1, lead(II) is in a nine coordinated sphere with seven oxygen atoms of the nitrate groups and thione sulfur, beta-nitrogen of neutral bidentate NS chelating ligand. Three nitrate groups act as bidentate chelating whereas the fourth nitrate group is coordinating to the central lead(II) and at the same time it bridges with neighboring lead(II) atom. Coordination geometry of the central lead(II) atom has a tricapped trigonal prismatic arrangement with streochemically inactive lone pair. The lead atoms are linked into polymeric chains and these chains form twin polymeric ribbons linked through bridging oxygen atoms. The N-H center dot center dot center dot O hydrogen bond network between N-SMDTC and O-nitrate atom leads to self-assembled molecular conformation and stabilizes the crystal structure. The complex 2 with similar spectral and thermal behavior is expected to have a tricapped trigonal prismatic structure. The thermal behavior studies shows that the complexes start to decompose at relatively low temperature (ca. 110 degrees C) to give PbS residue. (C) 2008 Elsevier B.V. All rights reservedclose1

Synthesis of nanocrystalline CdS from cadmium(II) complex of S-benzyl dithiocarbazate as a precursor

The single X-ray crystal structure of the cadmium(II) S-benzyl dithiocarbazate (SBDTC) complex. [Cd (SBDTC)Cl(2)](2), is reported. The compound has been found to be an effective single-source precursor for the preparation of CdS nanocrystals (NCs) via solvothermal method. CdS NCs including spheres and rods were prepared at a relatively low temperature by thermolysis of the precursor using chelating solvent like ethylene glycol (EG), ethylenediamine (EN), hydrazine hydrate (HH) or in a mixture of EG and EN. The influence of solvent, temperature and reaction time was investigated on the size and morphology of the NCs. Use of EG afforded spherical CdS NCs while EN uniquely yielded rod-shaped NCs, and mixture of spheres and rods are obtained from the mixture of EN and EG with a ratio 0.2 (v/v: EN/EG). UV-visible spectroscopy established pronounced quantum confinement with enhanced band gap and XRD analyses revealed hexagonal crystal phase for so obtained CdS NCs. The NCs were also characterized by transmission electron microscopy (TEM), photoluminescence spectroscopy (FL), energy-dispersive X-ray spectroscopy (EDS) and FTIR. The possible formation mechanism for the anisotropic growth of NCs was also discussed. (C) 2010 Elsevier Masson SAS. All rights reservedclose

Synthesis, spectroscopic characterization and thermal behavior of cadmium(II) complexes of S-methyldithiocarbazate (SMDTC) and S-benzyldithiocarbazate (SBDTC): X-ray crystal structure of [Cd(SMDTC)(3)] center dot 2NO(3)

Two new cadmium(II) complexes of the empirical formulae [Cd(SMDTC)(3)] center dot 2NO(3) (1) and [Cd(SBDTC)(2)]center dot 2NO(3) (2) have been synthesized and characterized by elemental analyses, UV-Vis, IR, (1)H NMR and TGA techniques. In Complex 1, the six coordination sites around cadmium are occupied by three neutral SMDTC molecules with N and S donor atoms from each ligand molecule, whereas in complex 2 the cadmium center is four coordinated with two relatively larger SBDTC ligands chelating with N and S donor atoms in the neutral thione form. In the solid state, thermal gravimetric analysis shows that both complexes are relatively volatile in nature and undergo facile thermal decomposition above 120 degrees C to form the metal sulfide followed by stepwise loss of ligand molecules. The crystal and molecular structure of complex I has been established by the X-ray diffraction method. The central cadmium(II) atom has an octahedral geometry with three five-membered chelate rings formed by SMDTC ligands. The crystal structure consists of parallel layers of cations and anions. The SMDTC molecules in cations are arranged with their N donor groups directed towards the anion layer in all alternating fashion and form hydrogen bonds with the O atoms of the anion. (C) 2008 Elsevier Ltd. All rights reservedclose1

Cu2S-deposited mesoporous NiO photocathode for a solar cell

The p-type Cu2S layer is deposited onto p-type mesoporous NiO electrode by spray pyrolysis deposition method using alcoholic solution of ethylenediamine-copper(II) complex and thiourea. A solar cell using Cu2S-deposited NiO mesoporous photocathode has been fabricated for the first time. The incident photon to current conversion efficiency (IPCE) values are found to be 0.8-1.8% for the newly designed NiO/Cu2S solar cell. It was shown that the p-type NiO/Cu2S structure could be successfully utilized to fabricate p-type solar cell and the possible mechanism for charge transfer is also discussed. (C) 2009 Published by Elsevier B. Vclose2