Search Results (32)

In the current research a series of new copper(II) complexes with novel acylhydrazone ligands were synthesized and their antibacterial and anticancer activities were determined. The complexes were characterized by molecular spectroscopy (FT-IR and UV-Vis) and conductivity measurements. Additionally, their structure was confirmed by single-crystal X-ray analysis. The crystallographic data revealed that all compounds are mononuclear Cu(II) species. The Cu(II) ion is four-coordinated by the ONO donor set from mono-deprotonated hydrazone ligand and one Cl^¯ anion, forming distorted square-planar geometry. The biological studies revealed that the compounds exhibit high antimicrobial activity, especially against Gram-positive bacteria, in some cases greater than the reference substances, and better activity than free ligands. The tested complexes possessed the lowest MIC and MBC values towards Staphylococcus epidermidis ATCC 12228 and Micrococcus luteus ATCC 10240. Furthermore, they showed no toxicity towards normal cell lines. Full article

A new copper(II) complex was synthesized using chromone-2-carboxylic acid as the main ligand, and coordinated pyridine molecules. The complex was successfully crystallized and structurally characterized by single crystal X-ray diffraction. This revealed a mononuclear structure with a distorted square pyramidal geometry around the central Cu(II) ion. The coordination sphere comprises oxygen atoms from the chromone moiety and nitrogen atoms from pyridine, resulting in a five-coordinate complex. A comprehensive physicochemical characterization was performed using Fourier transform infrared spectroscopy (FT-IR), UV–Vis spectroscopy, elemental (C, H, N), electrochemical (CV) and thermal analysis (TGA/DSC) to confirm the coordination environment and thermal stability of the compound. The complex exhibits distinct spectroscopic features indicative of ligand–metal charge transfer and d–d transitions typical of Cu(II) species. In addition, the synthesized complex was subjected to antimicrobial screening against Gram-positive and Gram-negative bacteria. The compound showed promising antibacterial activity, particularly against Escherichia coli, indicating its potential as a bioactive coordination compound. These results contribute to the growing body of research on metal-based chromone derivatives and emphasize the importance of copper complexes for the development of new antibacterial agents with defined crystal structures. Full article

2,2-Bis(3,5-dimethylpyrazol-1-yl)-1,1-diphenylethanol (HL) is a heteroscorpionate ligand capable of coordinating metal ions through two nitrogen atoms and one oxygen atom. We report a base free synthetic route to metal complexes of L and explore the resulting structural diversity. Notably, complex composition varies substantially depending on the metal ion, including dinuclear molybdenum species and distinct coordination behavior with silicon and copper. The isolated compounds include the dinuclear, oxygen-bridged complexes (LMoO₂)₂O and (LMoO)(μ-O)₂, as well as the mononuclear complexes LTi(NMe₂)₃, LZrCl₃, LGeCl₃, LWO₂Cl, LCu(acetate)₂H, and LSiMe₂Cl. Single crystal X-ray diffraction reveals that the bulky complex structures generate cavities in the crystal lattice, frequently occupied by solvent molecules. The titanium, zirconium, molybdenum, tungsten, and germanium complexes exhibit octahedral coordination, while structural peculiarities are observed for copper and silicon. The copper(II) complex shows a distorted octahedral geometry with one elongated ligand bond; the silicon complex is pentacoordinated in the solid state. Additional characterization includes melting points, NMR, and IR spectroscopy. The developed synthetic strategy provides a straightforward and versatile route to heteroscorpionate metal complexes. Full article

Pyridinecarbonitriles (pyCN), also referred to as cyanopyridines, are promising ligands for the formation of pyridine-based coordination compounds due to their two different N-donor atoms, which enable versatile coordination modes. Copper(II) complexes containing pyCN derivatives are of particular interest for their potential applications in medicinal chemistry and materials science. In this study, the synthesis, structural characterization, and thermal and magnetic properties of three new copper(II) complexes with 3-pyCN, 4-pyCN, and ethyl picolinimidate, obtained in situ by means of alcoholysis of 2-pyCN, are reported: [Cu₂(μ-Ac)₄(3-pyCN)₂] (1), [Cu(H₂O)₂(Etpic)₂]NO₃ (2), and [Cu(NO₃)₂(CH₃CN)(4-pyCN)₂]·CH₃CN (3). Single-crystal X-ray diffraction confirmed that complex 1 features a dinuclear paddle-wheel structure with bridging acetato ligands and monodentate 3-pyCN molecules, coordinated through the ring nitrogen, while complexes 2 and 3 are mononuclear. Thermal analysis showed an intense and highly exothermic decomposition of complex 3, containing nitrate ligands. Magnetic measurements revealed strong antiferromagnetic coupling in the dinuclear complex 1, whereas complexes 2 and 3 displayed paramagnetic behavior with effective magnetic moments ranging from 1.8 μ_B to 2.0 μ_B, consistent with isolated Cu(II) centers. Full article

The eight new copper(II), nickel(II), zinc(II), and iron(III) coordination compounds [Cu(L)Cl]₂ (1), [Cu(L)Br]₂ (2), [Cu(L)(NO₃)]₂ (3), [Cu(phen)(L)]NO₃ (4), [Ni(HL)₂](NO₃)₂·H₂O (5), [Ni(HL)₂]Cl₂ (6), [Zn(L)₂]·0.125H₂O (7), and [Fe(L)₂]Cl (8), where HL stands for 2-benzoylpyridine 4-allylthiosemicarbazone, were synthesized and characterized. ¹H, ¹³C NMR, and FTIR spectroscopies were used for characterization of the HL thiosemicarbazone. The elemental analysis, the FTIR spectroscopy, and the study of molar electrical conductivity were used for characterization of the coordination compounds 1–8. Also, the crystal structures of HL, its salts ([H₂L]Cl; [H₂L]NO₃), and complexes 1, 3, 5, 7, and 8 were determined using single-crystal X-ray diffraction analysis. Complexes 5, 7, 8 have mononuclear structures, while copper(II) complexes 1 and 3 have a dimeric structure with the sulfur atoms of the thiosemicarbazone ligand bridging two copper atoms together. Thiosemicarbazone HL and the complexes manifest antibacterial and antifungal activities. The studied substances are more active towards Gram-negative bacteria than towards Gram-positive bacteria and fungi. Complex 1 is the most active one towards Gram-positive bacteria and C. albicans, while the introduction of 1,10-phenanthroline into the inner sphere enhances the activity towards Gram-negative bacteria. Thiosemicarbazone and complexes 6 and 7 manifest antiradical activity that exceeds the activity of Trolox. HL and complex 1 manifest antiproliferative activity towards HL-60 cancer cells which exceeds the activity of their analogs with 2-formyl-/2-acetylpyridine 4-allylthiosemicarbazone. Full article

In this study, 3-chlorothiophene-2-carboxylic acid (HL) was used as a main ligand to successfully synthesize four novel complexes: [Cu(L)₂(Py)₂(OH₂)₂] (1), [Co(L)₂(Py)₂(OH₂)₂] (2) (Py = pyridine), [{Ni(L)₂(OH₂)₄}₂{Ni(L)(OH₂)₅}]L•5H₂O (3), and [{Co(L)₂(OH₂)₄}₂{Co(L)(OH₂)₅}]L•5H₂O (4). All four compounds were identified by elemental analysis and ESI mass spectrometry, and subsequently characterized by IR spectroscopy, UV-visible diffuse reflectance spectroscopy, electron paramagnetic resonance spectroscopy, thermogravimetric analysis, single-crystal X-ray crystallography, and cyclic voltammetry. X-ray analyses revealed that complexes 1 and 2 exhibit a centrosymmetric pseudo-octahedral coordination geometry; the copper (II) and cobalt (II) metal ions, respectively, are located at the crystallographic center of inversion. The coordination sphere of the copper (II) complex is axially elongated in accordance with the Jahn–Teller effect. Intriguingly, for charge neutrality, compounds 3 and 4 crystallized as three independent mononuclear octahedrally coordinated metal centers, which are two $\left[\mathrm{M}{\mathrm{L}}_2{\left({\mathrm{O}\mathrm{H}}_2\right)}_4\right]$ complex molecules and one ${\left[\mathrm{M}\mathrm{L}{\left({\mathrm{O}\mathrm{H}}_2\right)}_5\right]}^{+}$ complex cation (M = ${\mathrm{N}\mathrm{i}}^{\mathrm{I}\mathrm{I}}$ and ${\mathrm{C}\mathrm{o}}^{\mathrm{I}\mathrm{I}}$, respectively), with the ligand anion ${\mathrm{L}}^{-}$ serving as the counter ion. The anticancer activities of these complexes were systematically assessed on human leukemia K562 cells, lung cancer A549 cells, liver cancer HepG2 cells, breast cancer MDA-MB-231 cells, and colon cancer SW480 cells. Among them, complex 4 shows significant inhibitory effects on leukemia K562 cells and colon cancer SW480 cells. Full article

Three new complexes of copper(II) and chromone-2-carboxylic acid, a ligand from the group of hydroxypyrones, were synthesised according to the principles of green chemistry. The complexes were characterised by FT–IR and NMR spectroscopy, thermal and electrochemical analysis, and their structures are proposed. The results show the formation of mononuclear (1) and dinuclear hydroxo-bridged dinuclear copper(II) complexes (2 and 3). The results of cyclic voltammetry show that the copper in all complexes is in the +2-oxidation state. The antiproliferative activity was determined by MTT assay on 2D cell models in vitro on seven cell lines. The activity spectrum of complexes 1–3 ranged from the highest to the lowest value in the tumour cell lines tested, in the following order: Hep G2 > NCI-H358 > HT-29 > KATO III > MDA-MB 231 > Caco-2. The most effective concentration was 10⁻⁵ mol dm⁻³, which suppressed the growth of Hep G2 cells as follows: 69.5% (1), 64.8% (2) and 64% (3). The calculated selectivity index clearly shows that Hep G2 is the most sensitive cell line to copper complexes (SI = 1.623 (1); 1.557 (2), 1.431 (3). Full article

This study introduces a novel approach for enhancing the functional properties of cotton fibers through complexation of copper sulfate, and subsequent combination with chitosan (COT-CuSO₄-CTS). Our preliminary investigations focused on the development composites as candidate materials for functional coatings with antimicrobial properties. The materials were thoroughly characterized via scanning electron microscopy (SEM) and optical microscopy, providing insights into their structural features and composition. The findings show that the modified cotton materials exhibit potent antimicrobial activity. Specifically, the COT-CuSO₄ and COT-CuSO₄-CTS samples demonstrated zones of inhibition against both Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli, confirming their ability to reduce microbial growth significantly. The incorporation of a chitosan layer significantly enhanced the Ultraviolet Protection Factor (UPF) of the cotton fabric from 3.37 to over 50, indicating exceptional UV shielding capabilities, while copper(II) oxide treatment provided a moderate UPF value of 14.56. Blood compatibility studies further revealed that COT-CuSO₄ and COT-CuSO₄-CTS fabrics influence coagulation parameters, with a marked prolongation in activated partial thromboplastin time (aPTT) and prothrombin time (PT) compared to untreated cotton. This anticoagulant effect is primarily linked to the presence of copper, although the addition of chitosan modulates this response, slightly reducing clotting times compared to COT-CuSO₄ alone. Cytotoxicity and genotoxicity assessments using Peripheral Blood Mononuclear (PBM) cells indicated that untreated cotton was non-toxic and non-genotoxic. However, COT-CuSO₄ and COT-CuSO₄-CTS fabrics displayed a reduction in cell viability and induced DNA damage, highlighting their potential cytotoxic and genotoxic effects. Notably, COT-CuSO₄-CTS showed lower cytotoxicity and genotoxicity than COT-CuSO₄-CTS, suggesting that chitosan reduces the overall cytotoxic and genotoxic potential of the composite. Furthermore, plasmid DNA relaxation assays indicated that COT-CuSO₄ and COT-CuSO₄-CTS interact with DNA, with COT-CuSO₄ exhibiting a stronger interaction than COT-CuSO₄-CTS, consistent with the findings on PBM cells. Full article

This study investigates the activity of novel gold(I) and copper(I)/zinc(II) heteronuclear complexes against colon cancer. The synthesised heteronuclear Au(I)-Cu(I) and Au(I)-Zn(II) complexes were characterised and evaluated for their anticancer activity using human colon cancer cell lines (Caco-2). The complexes exhibited potent cytotoxicity, with IC₅₀ values in the low micromolar range, and effectively induced apoptosis in cancer cells. In the case of complex [Cu{Au(Spy)(PTA)}₂]PF₆ (2), its cytotoxicity is ×10 higher than its mononuclear precursor, while showing low cytotoxicity towards differentiated healthy cells. Mechanistic studies revealed that complex 2 inhibits the activity of thioredoxin reductase, a key enzyme involved in redox regulation, leading to an increase in reactive oxygen species (ROS) levels and oxidative stress, in addition to an alteration in DNA’s tertiary structure. Furthermore, the complexes demonstrated a strong binding affinity to bovine serum albumin (BSA), suggesting the potential for effective drug delivery and bioavailability. Collectively, these findings highlight the potential of the investigated heteronuclear Au(I)-Cu(I) and Au(I)-Zn(II) complexes as promising anticancer agents, particularly against colon cancer, through their ability to disrupt redox homeostasis and induce oxidative stress-mediated cell death. Full article

The catalytic properties of three copper complexes, [Cu(en)₂](ClO₄)₂ (1), [Cu(amp)₂](ClO₄)₂, (2) and [Cu(bpy)₂](ClO₄)₂ (3) (where en = ethylenediamine, amp = 2-aminomethylpyridine and bpy = 2,2′-bipyridine), were explored upon the oxidation of benzyl alcohol (BnOH). Maximized conversions of the substrates to their respective products were obtained using a multivariate analysis approach, a powerful tool that allowed multiple variables to be optimized simultaneously, thus creating a more economical, fast and effective technique. Considering the studies in a fluid solution (homogeneous), all complexes strongly depended on the amount of the oxidizing agent (H₂O₂), followed by the catalyst load. In contrast, time seemed to be statistically less relevant for complexes 1 and 3 and not relevant for 2. All complexes showed high selectivity in their optimized conditions, and only benzaldehyde (BA) was obtained as a viable product. Quantitatively, the catalytic activity observed was 3 > 2 > 1, which is related to the π-acceptor character of the ligands employed in the study. Density functional theory (DFT) studies could corroborate this feature by correlating the geometric index for square pyramid Cu(II)-OOH species, which should be generated in the solution during the catalytic process. Complex 3 was successfully immobilized in silica-coated magnetic nanoparticles (Fe₃O₄@SiO₂), and its oxidative activity was evaluated through heterogenous catalysis assays. Substrate conversion promoted by 3-Fe₃O₄@SiO₂ generated only BA as a viable product, and the supported catalyst’s recyclability was proven. Reduced catalytic conversions in the presence of the radical scavenger (2,2,6,6-tetrametil-piperidi-1-nil)oxil (TEMPO) indicate that radical and non-radical mechanisms are involved. Full article

The new diprotic ligand 3,5-di-tert-butylsalicylaldehyde 4-ethyl-3-thiosemicarbazone, abbreviated H₂(3,5-t-Bu₂)-sal4eT, exists as the thio-keto tautomer and adopts the E-configuration with respect to the imine double bond, as evidenced by single-crystal X-ray analysis and corroborated by spectroscopic characterisation. Upon treatment with Cu(OAc)₂·H₂O in the presence of either 2,9-dimethyl-1,10-phenanthroline (2,9-Me₂-phen) or 1,10-phenanthroline (phen) as a co-ligand in MeOH, this thiosemicarbazone undergoes conformational transformation (relative donor-atom orientations: syn,anti → syn,syn) concomitantly with tautomerisation and double deprotonation to afford the ternary copper(II) complexes [Cu{(3,5-t-Bu₂)-sal4eT}(2,9-Me₂-phen)] (1) and [Cu₂{3,5-t-Bu₂)-sal4eT}₂(phen)] (2). Crystallographic elucidation has revealed that complex 1 is a centrosymmetric dimer of mononuclear copper(II) complex molecules brought about by intermolecular H-bonding. The coordination geometry at the copper(II) centre is best described as distorted square pyramidal in accordance with the trigonality index (τ = 0.14). The co-ligand adopts an axial–equatorial coordination mode; hence, there is a disparity between its two Cu–N coordinate bonds arising from weakening of the apical one as a consequence of the tetragonal distortion. The axial X-band ESR spectrum of complex 1 is consistent with retention of this structure in solution. Complex 2 is a centrosymmetric dimer of dinuclear copper(II) complex molecules exhibiting intermolecular H-bonding and π-π-stacking interactions. The two copper(II) centres, which are 4.8067(18) Å apart and bridged by the thio-enolate nitrogen of the quadridentate thiosemicarbazonate ligand, display two different coordination geometries, one distorted square planar (τ₄ = 0.082) and the other distorted square pyramidal (τ₅ = 0.33). Such dinuclear copper(II) thiosemicarbazone complexes, which are crystallographically characterised, are extremely rare. In vitro, complexes 1 and 2 outperform cisplatin as antiproliferative agents in terms of potency and selectivity towards HeLa and MCF-7 cancer cell lines. Full article

The treatment of 2-(ArNC(H))C₆H₄-HNC₉H₆N with n-BuLi and the subsequent addition of CuCl₂ afforded the anilido-aldimine Cu(II) complexes 1-5 Cu[{2-[ArN=C(H)]C₆H₄}N(8-C₉H₆N)]Cl (Ar = 2,6-ⁱPr₂C₆H₃ (1), 2,4,6-(CH₃)₃C₆H₂ (2), 4-OCH₃C₆H₄ (3), 4-BrC₆H₄ (4), 4-ClC₆H₄ (5)), respectively. All the copper complexes were fully characterized by IR, EPR and HR-MS spectra. The X-ray diffraction analysis reveals that 2 and 4 are mononuclear complexes, and the Cu atom is sitting in a slightly square-planar geometry. These Cu(II) complexes have exhibited excellent catalytic activity in the Chan–Lam coupling reactions of benzimidazole derivatives with arylboronic acids, achieving the highest yields of up to 96%. Full article

The Cu(II)/Cu(I) conversion involves variation in the coordination number and geometry around the metal center. Therefore, the flexibility/rigidity of the ligand plays a critical role in the design of copper superoxide dismutase (SOD) mimics. A 1,3-Bis[(pyridin-2-ylmethyl)(propargyl)amino]propane (pypapn), a flexible ligand with an N₄-donor set, was used to prepare [Cu(pypapn)(ClO₄)₂], a trans-Cu(II) complex whose structure was determined by the X-ray diffraction. In DMF or water, perchlorate anions are exchanged with solvent molecules, affording [Cu(pypan)(solv)₂]²⁺ that catalyzes O₂^•− dismutation with a second-order rate constant k_McF = 1.26 × 10⁷ M⁻¹ s⁻¹, at pH 7.8. This high activity results from a combination of ligand flexibility, total charge, and labile binding sites, which places [Cu(pypapn)(solv)₂]²⁺ above other mononuclear Cu(II) complexes with more favorable redox potentials. The covalent anchoring of the alkyne group of the complex to azide functionalized mesoporous silica through “click” chemistry resulted in the retention of the SOD activity and improved stability. A dicationic Cu(II)-N₄-Schiff base complex encapsulated in mesoporous silica was also tested as an SOD mimic, displaying higher activity than the free complex, although lower than [Cu(pypapn)(solv)₂]²⁺. The robustness of covalently attached or encapsulated doubly charged Cu(II) complexes in a mesoporous matrix appears as a suitable approach for the design of copper-based hybrid catalysts for O₂^•− dismutation under physiological conditions. Full article

A combination of 4-styrylpyridine (spy) and 1-adamantanecarboxylic acid (Hadc) was employed in the assembly reactions with Zn(II) and Cu(II) nitrates. The photoreactivity of the products was compared and discussed on the basis of the structure–function relationship. Zinc(II) complex 1 is a trinuclear species of type [Zn₃(spy)₂(adc)₆] in which three zinc(II) atoms are linearly arranged, with two adjacent zinc(II) atoms linked by three bridging carboxylates. Two spy ligands occupy both terminal positions, yielding the overall structure of a six-bladed windmill. Copper(II) complex 2, [Cu(spy)₂(adc)₂][Cu₂(spy)₂(adc)₄]·2DMF, is an inorganic cocrystal comprising a mononuclear complex with a trans square planar geometry and a dinuclear complex with a paddle-wheel structure. In the photoreaction experiments characterized by ¹H NMR spectroscopy, the zinc(II) complex was found to be photoinert, while the copper(II) complex was photoreactive to form a cyclobutene ring via the [2+2] photodimerization between two spy ligands, resulting in the preparation of a one-dimensional chain as a coordination polymer. The separations of the C=C bond pair obtained from the crystal structures for both products also support their photoreactivity. For example, the spy ligands from two adjacent monocopper(II) complexes are aligned in a head-to-tail manner with the separation of 3.899 Å between the C=C bond pair, satisfying the so-called Schmidt criteria (<4.2 Å). However, no other products satisfy this condition. Full article

Copper(II) clusters of the type [Cu^II₄OCl₆L₄] (L = ligand or solvent) are a well-studied example of inverse coordination compounds. In the past, they have been studied because of their structural, magnetic, and spectroscopic features. They have long been believed to be redox-inactive compounds, but recent findings indicate a complex chemical equilibrium with diverse mononuclear as well as multinuclear copper(I) and copper(II) compounds. Furthermore, depending on the ligand system, such cluster compounds have proven to be versatile catalysts, e.g., in the oxidation of cyclohexane to adipic acid. This report covers a systematic study of the formation of [Cu^II₄OCl₆(TPP)₄] and [Cu^II₄OCl₆(TPPO)₄] (TPP = triphenylphosphine, PPh₃; TPPO = triphenylphosphine oxide, O=PPh₃) as well as the redox equilibrium of these compounds with mononuclear copper(I) and copper(II) complexes such as [Cu^IICl₂(TPPO)₂], [{Cu^IICl₂}₂(TPPO)₂], [{Cu^IICl₂}₃(TPPO)₂], [{Cu^II₄Cl₄}(TPP)₄], and [Cu^ICl(TPP)_n] (n = 1–3). Full article