Search Results (29)

The reaction of CuCl₂∙2H₂O, (E)-2-hydroxy-1,2-di(pyridin-2-yl)ethanone oxime (α-pyroxH₂) and Et₃N in refluxing MeOH gave complex [Cu₁₂Cl₁₂(mpydol)₄(pydox)₂(MeOH)₄] (1), where mpydol²⁻ is the dianion of 1,2-dimethoxy-1,2-di(pyridin-2-yl)ethane-1,2-diol and pydox²⁻ is the dianion of (E,E)-1,2-di(pyridin-2-yl)ethanedione dioxime. “Blind” experiments have proven that the transformation of α-pyroxH₂ is copper(II)-assisted. By changing the solvent from MeOH to MeCN, the polymeric compound {[Cu₄Cl₄(pic)₄]}_n (2) was isolated; pic⁻ is the pyridine-2-carboxylato(-1) ligand. The observed α-pyroxH₂ → pic⁻ transformation is also copper(II)-assisted. The topology of the metal ions in 1 can be described as consisting of four consecutive isosceles triangles in a zigzag configuration. Complex 2 is a 2D coordination polymer consisting of Cu^II₄ squares. Complete mechanistic views for the α-pyroxH₂ → mpydol²⁻, pydox²⁻ and pic⁻ transformations are critically discussed. In 1, the six Cu^II ions of the “central” triangles seem to be strongly antiferromagnetically coupled, thus cancelling out their spins ($S_{{\mathrm{Cu}}_6}$ = 0). The two local spins of S = 1/2 for each of the antiferromagnetically coupled “terminal” Cu^II₃ triangles result in an overall S = 1 ground state spin value for 1. In 2, the four Cu^II ions within each tetrameric unit are practically isolated and ferromagnetic interactions occur between these units through Cu^II–(μ-Cl)–Cu^II bridges. Full article

Structural rearrangements in metal–organic supramolecules constructed from the coordination of Cu(II) with m-xpt (m-xylylenebis(pyridyltriazole)) are investigated upon their interaction with 1,4-diazabicyclo[2.2.2]octane (dabco) and carbon dioxide-enriched air. The binuclear [Cu₂(m-xpt)₂]⁴⁺ complexes react with dabco to produce a carbonate-bridged trinuclear complex, [Cu₃(m-xpt)₃(µ-CO₃)]⁴⁺, and an oxalate-bridged binuclear complex, [Cu₂(m-xpt)₂(µ-C₂O₄)]²⁺, where carbonate and oxalate likely originate from CO₂ and dabco, respectively. The trinuclear complex reassembles the original dimer upon the removal of the carbonate ion. Similarly, polymeric [Cu(o-xpt)(PF₆)]_n, formed from Cu(I) and o-xpt (o-xylylenebis(pyridyltriazole)) coordination, undergoes oxidation in CO₂-enriched air to yield a tetranuclear Cu(II) complex, Cu₄(o-xpt)₃(μ₄-CO₃)(μ₂-OH)(μ₂-OCOCH₃)⁴⁺. The reaction progress is monitored by UV-Vis spectroscopy, and the major products are characterized by single-crystal X-ray diffraction. Full article

It is of great significance to clarify the corrosion mechanism of rust layers on bronze ware for appropriate conservation measures. In this study, the corrosion behavior of Cu-Sn bronze alloys in a 3.5 wt.% NaCl solution and a simulated archaeological soil solution was studied and compared using electrochemical measurements, microscopic observations, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The results showed that the presence of Cl⁻ was the key factor leading to the formation of harmful rust such as Cu₂(OH)Cl₃. In the NaCl solution, the rapid accumulation of Cl-containing corrosion products provided a certain degree of protection to Cu-Sn alloys, but the products easily fell off, thus increasing the continuous corrosion reactions again. This resulted in a significant increase in the corrosion rate of the alloy (i_corr from 4.845 μA·cm⁻² to 27.21 μA·cm⁻²) and a decrease in polarization resistance (R_p from 5.17 kΩ·cm² to 3.27 kΩ·cm²). In contrast, the corrosion reactions of the Cu-Sn alloy were dominated by complex ions other than Cl⁻ in archaeological soil environments, and the corrosion products tended to form stable and dense rust layers (i_corr was always lower than 1.6 μA·cm⁻², and R_p was maintained above 24 kΩ·cm²), which improved corrosion resistance by two orders of magnitude compared to the unstable rust layer that formed in NaCl solution. In addition, Cl-containing corrosion products boosted the wettability of rust layers, thereby facilitating penetration of corrosive media that strengthened corrosion reactions. This study deepens our understanding of the degradation mechanisms of bronze artifacts and provides a scientific basis for developing bronze conservation strategies. Full article

The copper(II) complexes of general formula [Cu(^GL2^H,H)(Cl)] (A4–A6, G = NO₂, H and OMe, respectively), bearing NNO tridentate Schiff base ligands (^GL2^H,H)⁻ derived from the mono-condensation of 1,3-diaminopropane and G-substituted salicylaldehydes, are here reported. The elongation of the diamine with one additional carbon atom with respect to the triad derived from ethylenediamine [Cu(^GL1^H,H)(Cl)] (A1–A3, G = NO₂, H and OMe, respectively) led to different synthetic procedures, with the difficult isolation of A6 that could be obtained only in few crystals suitable for X-ray diffractions. Operating in acidic conditions to promote the coordination of chloride and expulsion of pyridine from the complex [Cu(^GL2^H,H)(py)](ClO₄) (G = NO₂) allows for obtaining A4. On the other hand, structural rearrangement occurs when G = H, yielding the dinuclear species [Cu₂(μ-saltn)(^HL2^H,H)](ClO₄)⋅0.5MeOH (D5⋅0.5MeOH) instead of the desired A5, which can be obtained by avoiding the use of HCl and operating in the excess of LiCl. Finally, A4 and A5 were investigated as cytotoxic agents against malignant (MDA-MB-231 and 22-Rv1) and healthy (HaCaT) cell lines, and the ability of the most promising A5 to be internalized and interact with cellular targets was studied. Full article

Dechlorination is a crucial strategy for archeological bronze stabilization to resist corrosion induced by cuprous chloride (CuCl). Conventional samples, either archeological or simulated ones, have deficiencies in revealing dechlorination mechanisms for their complex rust layers and difficulties in quantifying chlorine content. In this work, samples with fixed chlorine amounts were prepared by compressing method to solve overcomplicated and unquantifiable problems. Then, patina profiles and desalinization solutions were analyzed to revisit the dechlorination mechanism across varying solution concentrations and current densities after dechlorination treatments. Results indicate that the sodium hydroxide (NaOH) desalinization method is achieved by converting CuCl to trihydroxychloride (Cu₂(OH)₃Cl). However, this transformation leads to an expansion of the CuCl layer, nearly doubling the CuCl layer thickness at the current density of 25 μA/cm². Dechlorination solution measurements provide information on quantifying chlorine removal and dechlorination progress. Theoretically, the endpoint (c₀) for the NaOH dechlorination method is supposed to be a chloride ion concentration of 358.2 ppm. As the NaOH solution concentrations vary from 10⁻⁶ to 10⁻², CuCl dechlorination progress (E_t=24h) calculations are at about 3% to 6% at 24 h. Applying the current significantly improves the effectiveness of dechlorination at 2.5 μA/cm². However, the chloride ion concentration in the solution starts to decrease after reaching a current density of 12.5 μA/cm², even dropping to 12.07 ppm at 25 μA/cm². According to a theoretical analysis, chlorine evolution during electrolytic processes would be responsible for this phenomenon. Full article

The molecular and supramolecular structures of some M(II) complexes (M = Co, Mn, Cu, Ni, Zn) with a hydrazone-s-triazine ligand (^BMPyTr) were discussed based on single crystal X-ray diffraction (SCXRD), Hirshfeld and DFT analyses. A new Co(II) complex of the same ligand was synthesized and its structure was confirmed to be [Co(^BMPyTr)Cl₂]·H₂O based on FTIR and UV–Vis spectra, elemental analysis and SCXRD. The geometry around Co(II) was a distorted square pyramidal configuration (τ₅ = 0.4), where Co(II) ion is coordinated to one NNN-tridentate ligand (^BMPyTr) and two Cl^- ions. A Hirshfeld analysis indicated all potential contacts within the crystal structure, where the percentages of O⋯H, N⋯H, C⋯H, and H⋯H contacts in one unit were 11.2, 9.3, 11.4, and 45.9%, respectively, while the respective values for the other complex unit were 10.3, 8.8, 10.6, and 48.0%. According to DFT calculations, the presence of strongly coordinating anions, such as Cl^-, in addition to the large metal ion size, were found to be the main reasons for the small M-^BMPyTr interaction energies in the cases of [Mn(^BMPyTr)Cl₂] (260.79 kcal/mol) and [Co(^BMPyTr)Cl₂]·H₂O (307.46 kcal/mol) complexes. Interestingly, the Co(II) complex had potential activity against both Gram-positive (S. aureus and B. subtilis) and Gram-negative (E. coli and P. vulgaris) bacterial strains with inhibition zone diameters of 13, 15, 16, and 18 mm, respectively. Also, the new [Co(^BMPyTr)Cl₂]·H₂O (IC₅₀ = 131.2 ± 6.8 μM) complex had slightly better cytotoxic activity against HCT-116 cell line compared to ^BMPyTr (145.3 ± 7.1 μM). Full article

A new complex of copper(II) with methyl-5-(trifluoromethyl)pyrazol-3-yl-ketazine (H₂L) was synthesized with the composition [Cu₂L₂]∙C₂H₅OH (1). Recrystallization of the sample from DMSO yielded a single crystal of the composition [Cu₂L₂((CH₃)₂SO)] (2). The coordination compounds were studied by single-crystal X-ray diffraction analysis, IR spectroscopy, and static magnetic susceptibility method. The data obtained indicate that the polydentate ligand is coordinated by both acyclic nitrogen and heterocyclic nitrogen atoms. The cytotoxic activity of the ligand and complex 1 was investigated on human cell lines MCF7 (breast adenocarcinoma), Hep2 (laryngeal carcinoma), A549 (lung carcinoma), HepG2 (hepatocellular carcinoma), and MRC5 (non-tumor lung fibroblasts). The complex was shown to have a pronounced dose-dependent cytotoxicity towards these cell lines with LC₅₀ values in the range of 0.18–4.03 μM. Full article

ERI and SSZ-13 were subjected to post-synthetic treatments (depending on the zeolite topology) to create micro-/mesoporous materials. The results in terms of NH₃-SCR-DeNO_x show that the applied treatments improved the catalytic activity of the Cu-containing ERI-based materials; however, the NO conversion did not vary for the different materials treated with NaOH or NaOH/HNO₃. For the micro-/mesoporous Cu-containing SSZ-13, a lower NO conversion in NH₃-SCR-DeNO_x was observed. Thus, our findings challenge the current paradigm of enhanced activity of micro-/mesoporous catalysts in NH₃-SCR-DeNO_x. The modification of the supports results in the presence of different amounts and kinds of copper species (especially isolated Cu²⁺ and aggregated Cu species) in the case of ERI- and SSZ-13-based samples. The present copper species further differentiate the formation of reactive reaction intermediates. Our studies show that besides the μ-η²,η²-peroxo dicopper(II) complexes (verified by in situ DR UV-Vis spectroscopy), copper nitrates (evidenced by in situ FT-IR spectroscopy) also act as reactive intermediates in these catalytic systems. Full article

Steroids are often considered valuable molecular tools for the development of anticancer agents with improved pharmacological properties. Conjugation of metal chelating moieties with a lipophilic sterane backbone is a viable option to obtain novel anticancer compounds. In this work, two estradiol-based hybrid molecules (PMA-E2 and DMA-E2) with an (N,N,O) binding motif and their Cu(II) complexes were developed. The lipophilicity, solubility, and acid-base properties of the novel ligands were determined by the combined use of UV-visible spectrophotometry, pH-potentiometry, and ¹H NMR spectroscopy. The solution speciation and redox activity of the Cu(II) complexes were also investigated by means of UV-visible and electron paramagnetic resonance spectroscopy. Two structurally analogous ligands (PMAP and DMAP) were also included in the studies for better interpretation of the solution chemical data obtained. Three pK_a values were determined for all ligands, revealing the order of the deprotonation steps: pyridinium-NH⁺ or NH(CH₃)₂⁺, secondary NH₂⁺, and OH. The dimethylamine derivatives (DMA-E2, DMAP) are found in their H₂L⁺ forms in solution at pH 7.4, whereas the fraction of the neutral HL species is significant (34–37%) in the case of the pyridine nitrogen-containing derivatives (PMA-E2, PMAP). Both estradiol derivatives were moderately cytotoxic in human breast (MCF-7) and colon adenocarcinoma (Colo-205) cells (IC₅₀ = 30–63 μM). They form highly stable complexes with Cu(II) ions capable of oxidizing ascorbate and glutathione. These Cu(II) complexes are somewhat more cytotoxic (IC₅₀ = 15–45 μM) than their corresponding ligands and show a better selectivity profile. Full article

The synthesis and structural characterization of a new triangular Cu₃–μ₃OH pyrazolato complex of formula, [Cu₃(μ₃−OH)(pz)₃(Hpz)₃][BF₄]₂ (1−Cu₃), Hpz = pyrazole, is presented. The triangular unit forms a quasi-isosceles triangle with Cu–Cu distances of 3.3739(9), 3.3571(9), and 3.370(1) Å. This complex is isostructural to the hexanuclear complex [Cu₃(μ₃−OH)(pz)₃(Hpz)₃](ClO₄)₂]₂ (QOPJIP). A comparative structural analysis with other reported triangular Cu₃–μ₃OH pyrazolato complexes has been carried out, showing that, depending on the pyrazolato derivative, an auxiliary ligand or counter-anion can affect the nuclearity and/or the dimensionality of the system. The magnetic properties of 1−Cu₃ are analyzed using experimental data and DFT calculation. A detailed analysis was performed on the magnetic properties, comparing experimental and theoretical data of other molecular triangular Cu₃–μ₃OH complexes, showing that the displacement of the μ₃−OH⁻ from the Cu₃ plane, together with the type of organic ligands, influences the nature of the magnetic exchange interaction between the spin-carrier centers, since it affects the overlap of the magnetic orbitals involved in the exchange pathways. Finally, a detailed comparison of the magnetic properties of 1−Cu₃ and QOPJIP was carried out, which allowed us to understand the differences in their magnetic properties. Full article

A selection of dimeric Cu(II) complexes with bidentate N,N′ ligands with the general formula [Cu(L)(X)(μ-OH)]₂·nH₂O and [Cu(L)(μ-OH)]₂X₂·nH₂O were magneto-structurally analyzed using the Density Functional Theory (DFT). A Broken Symmetry-Density Functional Theory (BS-DFT) study was undertaken for these complexes with relevant decomposition schemes that gave insight into the effect of the nature of the ligand and coordination environment on the DFT-predicted coupling constants (J). The impact of the spin population, which correlates well with the Cu-O-Cu bridging angles and the calculated coupling constant (J) values, was studied. The models were further refined using a complete active space self-consistent field (CASSCF) while expanding the active space from 2 orbitals 2 electrons (2,2) to 10 orbitals 18 electrons (18,10). These models were approximated using multireference methods (n-electron valence state perturbation theory and difference dedicated configuration interaction), and a better approximation of J values was found as expected. Orbitals involved in the superexchange pathway were also visualized. Full article

Controlling and understanding the Cu-catalyzed homocoupling reaction is crucial to prompt the development of efficient Cu-catalyzed cross-coupling reactions. The presence of a coordinating base (hydroxide and methoxide) enables the B-to-Cu(II) transmetalation from aryl boronic acid to Cu^IICl₂ in methanol, through the formation of mixed Cu-(μ-OH)-B intermediates. A second B-to-Cu transmetalation to form bis-aryl Cu(II) complexes is disfavored. Instead, organocopper(II) dimers undergo a coupled transmetalation-electron transfer (TET) allowing the formation of bis-organocopper(III) complexes readily promoting reductive elimination. Based on this mechanism some guidelines are suggested to control the undesired formation of homocoupling product in Cu-catalyzed cross-coupling reactions. Full article

Conditions have been identified in which phenolic aldoximes and ketoximes of the types used in commercial solvent extraction processes can be doubly deprotonated and generate polynuclear Cu complexes with lower extractant:Cu molar ratios than those found in commercial operations. Electrospray mass spectrometry has provided an insight into the solution speciation in extraction experiments and has identified conditions to allow isolation and characterization of polynuclear Cu-complexes. Elevation of pH is effective in enhancing the formation of trinuclear complexes containing planar {Cu₃-μ₃-O}⁴⁺ or {Cu₃-μ₃-OH}⁵⁺ units. DFT calculations suggest that such trinuclear complexes are more stable than other polynuclear species. Solid structures of complexes formed by a salicylaldoxime with a piperidino substituent ortho to the phenolic OH group (L⁹H₂) contain two trinuclear units in a supramolecular assembly, {[Cu₃OH(L⁹H)₃(ClO₄)](ClO₄)} ₂, formed by H-bonding between the central {Cu₃-μ₃-OH}⁵⁺ units and oxygen atoms in the ligands of an adjacent complex. Whilst the lower ligand:Cu molar ratios provide more efficient Cu-loading in solvent extraction processes, the requirement to raise the pH of the aqueous phase to achieve this will make it impractical in most commercial operations because extraction will be accompanied by the precipitation (as oxyhydroxides) of Fe(III) which is present in significant quantities in feed solutions generated by acid leaching of most Cu ores. Full article

A new ligand 5-((1-methyl-pyrrol-2-yl) methyl)-4-(naphthalen-1-yl)-1,2,4-triazoline-3-thione (C15) and its metal complexes with formulae: Mn(C15)Cl₂MeOH (1), Fe(C15)Cl₂MeOH (2), Ni(C15)Cl₂MeOH (3), Cu(C15)₂Cl₂ (4) and Zn(C15)₄Cl₂ (5) have been synthesized. The C15 ligand and complexes were characterized by NMR, elemental analysis, FT-IR, EPR, magnetic and TGA studies. The anticancer activities of the organic ligand (C15) and complexes (1–5) were evaluated against human colon adenocarcinoma (HT29) and human lung (A549) cancer cell lines. The complex (1) exhibited potential activity at concentration of 794.37 μM (A549) and 654.31 μM (HT29) in both cancer cells. The complex (3) showed significant activity against the HT29 cancer cell line with an IC₅₀ value of 1064.05 μM. This article highlights some of the metals that have become important in the development of new coordination complexes and the treatment of cancer. Additionally, for C15, the toxicity was predicted by ADMET analysis and molecular docking. Full article

A series of new heteroleptic copper(II) complexes of the composition [Cu(L)(bpy)]NO₃·2MeOH (1), [Cu(L)(dimebpy)]NO₃·2H₂O (2), [Cu(L)(phen)]NO₃·2MeOH (3), [Cu(L)(bphen)]NO₃·MeOH (4), [Cu(L)(dppz)]NO₃·MeOH (5) was prepared, where HL = 3-(3,4-dihydroxyphenyl)-5-hydroxy-8,8-dimethyl-6-(3-methylbut-2-ene-1-yl)-4H,8H-benzo[1,2-b:3,4-b′]dipyran-4-one, (pomiferin) and bpy = 2,2′-bipyridine, dimebpy = 4,4′-dimethyl-2,2′-bipyridine, phen = 1,10-phenanthroline, bphen = 4,7-diphenyl-1,10-phenanthroline, and dppz = dipyrido[3,2-a:2′,3′-c]phenazine. The complexes were characterized using elemental analysis, infrared and UV/Vis spectroscopies, mass spectrometry, thermal analysis and conductivity measurements. The in vitro cytotoxicity, screened against eight human cancer cell lines (breast adenocarcinoma (MCF-7), osteosarcoma (HOS), lung adenocarcinoma (A549), prostate adenocarcinoma (PC-3), ovarian carcinoma (A2780), cisplatin-resistant ovarian carcinoma (A2780R), colorectal adenocarcinoma (Caco-2) and monocytic leukemia (THP-1), revealed the complexes as effective antiproliferative agents, with the IC₅₀ values of 2.2–13.0 μM for the best performing complexes 3 and 5. All the complexes 1–5 showed the best activity against the A2780R cells (IC₅₀ = 2.2–6.6 μM), and moreover, the complexes demonstrated relatively low toxicity on healthy human hepatocytes, with IC₅₀ > 100 μM. The complexes were evaluated by the Annexin V/propidium iodide apoptosis assay, induction of cell cycle modifications in A2780 cells, production of reactive oxygen species (ROS), perturbation of mitochondrial membrane potential, inhibition of apoptosis and inflammation-related signaling pathways (NF-κB/AP-1 activity, NF-κB translocation, TNF-α secretion), and tested for nuclease mimicking activity. The obtained results revealed the corresponding complexes to be effective antiproliferative and anti-inflammatory agents. Full article