•The simple and facile approach to copper coordination polymers exhibiting optoelectronic properties and Catecholase-like activity.•The complexes 1 and 2 are μ1,3-azido bridged 1D polymeric chains ...and complex 3 is μ1,1-azido bridged dimeric discrete molecule.•The dc current-voltage characteristics of Al-complex 1/2/3 -Al structures have shown non linear trends under dark and illumination conditions.•The complexes can act as potential catalysts for the Catecholase-like activity.
A series of new copper(II)-azido complexes of 1D polymeric chains of Cu(L1)(μ1,3-N3)n (1) and Cu(L2)(μ1,3-N3)n (2), and binuclear Cu(L3)(μ1,1-N3)2 (3) HL1 = N-butyl-N-(5-bromosalcylidine)ethane-1,2-diamine, HL2 = N-butyl-N-(5-chlorosalcylidine)ethane-1,2-diamine, HL3 = N-butyl-N-(salcylidine)ethane-1,2-diamine have been synthesized and characterized. Characterizations of 1–3 have been accomplished by usual physico-chemical techniques such as elemental analysis, FTIR, UV–vis and single crystal X-ray diffraction studies. X-ray diffraction analyses of 1 and 2 reveal that the monomeric units of 1D polymers are interconnected via the μ1,3-azido bridging. The coordination geometry around the copper(II) centers in 1 and 2 can be best described as distorted square pyramidal environments. Complex 3 shows a centrosymmetric structure with two copper(II) centers that are held together by μ1,1-azido bridging in a distorted square pyramidal environment. In the electrical studies of 1–3, both direct current (dc) and alternating current (ac) analyses have been carried out based on the metal-complex (1/2/3)-metal (M-S-M) structures. The sheet resistance of the deposited films and the metal-complex contact resistance are estimated by employing transfer length method (TLM) measurements. The dark current-voltage characteristics of Al-complex (1/2/3)-Al structures are analyzed by considering dual back-to-back Schottky barrier diode structure. The voltage variations of the device current under illumination (400–700 nm) clearly demonstrate the photo-sensitivity of these materials. The catalytic activities of 1–3 have been investigated towards aerial oxidation of 3,5-di-tert-butylcatechol. All three complexes exhibit potential catalytic effectiveness towards oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC) to 3,5-di-tert-butyl-o-quinone (3,5-DTBQ) with turnover numbers 14.76, 33.92 and 81.02 h−1 for 1, 2 and 3, respectively.
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The present article demonstrates the simple and facile approach to prepare three copper coordination polymers exhibiting optoelectronic properties and Catecholase-like activity.
In this manuscript, a new colorimetric and fluorescent chemosensor (T) was designed and synthesized, it could successively detect Cu2+ and H2PO4− in DMSO/H2O (v/v=9:1, pH=7.2) buffer solution with ...high selectivity and sensitivity. When added Cu2+ ions into the solution of T, it showed a color changes from yellow to colorless, meanwhile, the green fluorescence of sensor T quenched. This recognition behavior was not affected in the presence of other cations, including Hg2+, Ag+, Ca2+, Co2+, Ni2+, Cd2+, Pb2+, Zn2+, Cr3+, and Mg2+ ions. More interestingly, the Cu2+ ions contain sensor T solution could recover the color and fluorescence upon the addition of H2PO4− anions in the same medium. And other surveyed anions (including F−, Cl−, Br−, I−, AcO−, HSO4−, ClO4−, CN− and SCN−) had nearly no influence on the recognition behavior. The detection limits of T to Cu2+ and T-Cu2+ to H2PO4− were evaluated to be 1.609×10−8M and 0.994×10−7M, respectively. In addition, the sensor T also could be served as a recyclable component and the logic gate output was also defined in sensing materials. The test strips based on sensor T were fabricated, which acted as a convenient and efficient Cu2+ and H2PO4− test kits.
A specially selectivity and highly sensitivity ON-OFF-ON reversible chemosensor T based on imine bound as the recognize side and N,N-diethyl as the fluorescence signal report group had been designed and synthesized. Display omitted
•A highly selective and sensitive reversible fluorescent sensor for detecting Cu2+ and H2PO4− in aqueous media.•The change of recognition process can be detected by naked eyes.•The test strips could conveniently detect Cu2+ and H2PO4− in aqueous media.
A bridged dinuclear Schiff base-type copper(II) complex, (Cu2(L2)2CH3COO)2Cu(NO3)4·2CH3COOCH2CH3 has been synthesized via complexation of Cu(II) nitrate trihydrate with HL1. During the reaction, the ...C–N bond in the HL1 is converted into the CN–OH group in the ligand HL2. The Cu(II) complex was analyzed using IR and UV–Vis spectroscopy, elemental analysis and single-crystal X-ray crystallography. The spectroscopic data of the Cu(II) complex was compared with the ligand HL1. In the crystal, each complex links with four other molecules into an infinite 2-D supramolecular structure through intermolecular hydrogen bonding and π⋯π stacking interactions. Moreover, the electrochemical properties of HL1 and Cu(II) complex have been studied by cyclic voltammetry. Electron paramagnetic resonance (EPR) spectroscopy of the bridged dinuclear Cu(II) complex was also investigated. The geometries and electronic properties of both the ligand HL1 and the Cu(II) complex were studied by DFT calculation. Display omitted
•A bridged dinuclear Cu(II) complex has been synthesized and characterized structurally.•The spectroscopic data of the Cu(II) complex was compared with the ligand HL1.•The electrochemical properties of HL1 and the complex have been studied by cyclic voltammetry.•EPR spectroscopy of the bridged dinuclear Cu(II) complex was also investigated.•The geometries and electronic properties of both HL1 and the complex were studied by DFT calculation.
A bridged dinuclear Schiff base-type copper(II) complex, (Cu2(L2)2CH3COO)2Cu(NO3)4·2CH3COOCH2CH3 (HL2=1-(2-{(E)-3,5-dibromo-2-hydroxybenzylideneamino}phenyl)ethanone oxime), has been synthesized via complexation of Cu(II) nitrate trihydrate with HL1 (2-(3,5-dibromo-2-hydroxyphenyl)-4-methyl-1,2-dihydroquinazoline-3-oxide, H is the deprotonatable hydrogen). During the reaction, the C–N bond in the HL1 is converted into the CN–OH group in the ligand HL2. The Cu(II) complex was analyzed using IR and UV–Vis spectroscopy, elemental analysis and single-crystal X-ray crystallography. The spectroscopic data of the Cu(II) complex was compared with the ligand HL1. In the crystal, each complex links with four other molecules into an infinite 2-D supramolecular structure through intermolecular hydrogen bonding and π⋯π stacking interactions. Moreover, the electrochemical properties of HL1 and Cu(II) complex have been studied by cyclic voltammetry. The powder EPR spectrun of the dinuclear Cu(II) complex indicated that the existence of an antiferromagnetic spin-spin interaction between the magnetically nonequivalent two Cu(II) ions. The geometries and electronic properties of both the ligand HL1 and the Cu(II) complex were studied by DFT calculation.
Three novel hybrid inorganic-organic copper(II) 2,4,5-trichlorophenoxyacetate complexes Cu(γ-pic)3(L)2·H2O 1, trans-Cu(en)2(L)2·2H2O 2 and Cu2(H2tea)2(L)2·2H2O 3 have been synthesized and ...characterized by elemental analyses, TGA, spectroscopic techniques (IR, UV/VIS and EPR), conductance measurements, magnetic susceptibility studies and single crystal X-ray structure determination. The crystal lattice is stabilized by framework of supramolecular interactions.
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•Three novel hybrid copper(II) 2,4,5-trichlorophenoxyacetate complexes were synthesized.•Crystal lattice is stabilized by array of non-covalent interactions.•All complexes show similar mode of carboxylate coordination (monodentate).•Variety of structural frameworks in presence of different ligands.•Complex 2 shows dual nature (ionic in solution state and covalent in solid state).
Three novel coordination complexes of copper(II) with 2,4,5-trichlorophenoxyacetate Cu(γ-pic)3(L)2·H2O 1, trans-Cu(en)2(L)2·2H2O 2 and Cu2(H2tea)2(L)2·2H2O 3, where L=2,4,5-trichlorophenoxyacetate, γ-pic=γ-picoline, en=ethylenediamine, H2tea=monodeprotonated triethanolamine, were synthesized by addition of γ-picoline/ethylenediamine/triethanolamine, respectively, to the hydrated Cu(2,4,5-trichlorophenoxyacetate)2 suspended in methanol-water (4:1, v/v). The newly synthesized complexes have been characterized by elemental analyses, spectroscopic techniques (UV–Vis and FT-IR), magnetic moment determination, molar conductance studies, TGA and single crystal X-ray diffraction method. The structure determination revealed neutral nature of complexes in all the three cases, with different coordination geometry around the copper(II) metal centre depending upon nature of the N- or N,O-donor ligands. Hydrogen bonding network i.e. O–H⋯O and C–H⋯O in complexes 1, 3 and N–H⋯O, and O–H⋯O in complex 2 stabilizes crystal lattice in copper(II) complexes besides other non-covalent interactions.
A new binuclear copper(II) complex with unusual triple bridging of hydryxido-, nitrato- and phenoxido-groups is synthesized with a compartmental ligand and presented with structural analysis, ...Hirshfeld surface analysis, theoretical calculation along with the catalytic CuAAC click reaction in aqueous phase.
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•A binuclear copper complex with simultaneous triple bridging of hydroxide, phenoxide, and nitrate anion has been synthesized.•Molecular and supramolecular structure of the complex has been analysed in details in collaboration with Hirshfeld surface analysis and theoretical study.•The blue-luminescent complex has also been used in copper catalyzed azide–alkyne cycloaddition reaction in water.
Catalytic click reactions are highly fascinating in chemical industries from several aspects like green synthesis, easy separation, nearly-perfect bond formation, etc. A new binuclear copper complex Cu2(µ-OH)(µ-NO3)(H4L)(H2O)(NO3)·(H2O) (where H5L = 2,2′-((1E,1′E)-((2-hydroxy-5-methyl-1,3-phenylene)bis(methanylylidene))bis(azanylylidene))bis(propane-1,3-diol)) has been used for catalytic Huisgen 1,3-dipolar cycloaddition click reaction in water. The complex has been synthesized by using a multidentate compartmental ligand and characterized by single crystal X-ray crystallography along with spectral characterizations. The structural analysis shows that this binuclear complex crystallizes in the monoclinic space group P21/c and both metal centers are bridged by a nitrate anion, a hydroxide ion, and a phenoxide group. Each discrete complex is connected by hydrogen bonding interactions to form a 3D supramolecular structure. Hirshfeld analysis and corresponding 2D fingerprint plots give a detailed information about the intermolecular interactions present in the complex. The complex also shows blue emission spectra. Density functional theory (DFT) and time dependent DFT (TDDFT) calculations have been carried out to rationalize the geometry and absorption spectrum of the complex. Afterward, the complex was used for the green catalytic click chemistry by optimizing the Huisgen 1,3-dipolar cycloaddition reaction. The complex shows high catalytic activity for copper catalyzed azide–alkyne cycloaddition (CuAAC) reaction in the aqueous phase with an average 80 % yield.
Metal complexes have gained significant attention as potential anti-cancer agents. The anti-cancer activity of Co(phen)
(MeATSC)(NO
)
•1.5H
O•C
H
OH
(where phen = 1,10-phenanthroline and MeATSC = ...9-anthraldehyde-
(4)-methylthiosemicarbazone) and Cu(acetylethTSC)ClCl•0.25C
H
OH
(where acetylethTSC =
-ethyl-2-1-(thiazol-2-yl)ethylidenehydrazinecarbothioamide) was investigated by analyzing DNA cleavage activity. The cytotoxic effect was analyzed using CCK-8 viability assay. The activities of caspase 3/7, 9, and 1, reactive oxygen species (ROS) production, cell cycle arrest, and mitochondrial function were further analyzed to study the cell death mechanisms. Complex
induced a significant increase in nicked DNA. The IC
values of complex
were 17.59 μM and 61.26 μM in cancer and non-cancer cells, respectively. The IC
values of complex
were 5.63 and 12.19 μM for cancer and non-cancer cells, respectively. Complex
induced an increase in ROS levels, mitochondrial dysfunction, and activated caspases 3/7, 9, and 1, which indicated the induction of intrinsic apoptotic pathway and pyroptosis. Complex
induced cell cycle arrest in the S phase, ROS generation, and caspase 3/7 activation. Thus, complex
induced cell death in the breast cancer cell line
activation of oxidative stress which induced apoptosis and pyroptosis while complex
induced cell cycle arrest through the induction of DNA cleavage.
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•CU(II) complexes were derived from NNN and NNO Schiff Base ligands.•They are characterized by UV-Vis, FTIR, ESI-MS spectroscopic studies.•Crystal study, photodegradation, BSA ...interaction, cell viability studies were done.•The results showed their efficiency as photodegradation agents for Methylene Blue.•They can also be used as biomaterial transplants.
Herein, a monomeric copper(II) complex of the general formula Cu(L)Cl2 (1) and a polymeric copper(II) complex bearing the formula Cu2L/2(µ-N3)(N3)n, (2) have been synthesized using NNN and NNO tridentate Schiff base ligands, L and L/ where L = N-((6-methoxypyridin-2-yl)methylene)(piperidin-2-yl)methane amine and L/ = 1-((3-(methylamino)propylimino)methyl)naphthalene-2-ol. Both the complexes have been characterized by single crystal X-ray diffraction and UV–Vis, FTIR, ESI-MS spectroscopic studies. The crystal structure of the complex (1) reveals a square pyramidal geometry whereas the structure of the complex (2) exhibits elongated square pyramidal geometry and the asymmetric unit of the complex contains two Cu(II) ions connected by the single µ-azido bridge. The electronic structures of the complexes are optimized by Density Functional Theory (DFT) calculations to explore their coordination stabilities and chemically reactive parameters. Besides, the Hirshfeld surfaces and two-dimensional fingerprint plot are also carried out to visualize the intermolecular interactions in the crystal of complex 1 and complex 2. Photodegradation against Methylene Blue (MB) proves the greater efficiency of complex 2 as a photodegradation agent for MB organic pollutant dye. Preferential binding studies of both the complexes towards the protein, Bovine Serum Albumin (BSA), by a series of spectroscopic techniques reveal that complex 1 strongly interacts with BSA. The spectroscopic data are well correlated by molecular docking studies. These interaction studies prompted us for cell viability studies against SiHa cancer cell to check whether the complexes may be used as biomaterial transplants or not. It is observed that the cell viability increases with time demonstrating the biocompatible nature of the complexes as well as their uses as biomaterial transplants.
Five complexes, Cu(L)2·4.5H2O (1), Cu(HL)2(NO3)2·CH3OH (2) {Cu2(L)2(NO3)(H2O)2·(NO3)}n (3), Cu2(HL)2(SO4)2·2CH3OH (4) and Cu4(L)4Cl4·5H2O (5) based on HL (where HL = 2-acetylpyrazine isonicotinoyl ...hydrazone) have been synthesized and characterized by X-ray diffraction analyses. The counter anion and organic base during the synthesis procedure influence the structures of the complexes efficiently, which generate five complexes as mono-, bi-, tetra-nuclear and one-dimensional structures. The antitumor activities of the complexes 1–5 (except for complex 3 with the poor solubility) against the Patu8988 human pancreatic cancer, ECA109 human esophagus cancer and SGC7901 human gastric cancer cell lines are screened by MTT assay. The results indicate that the chelation of Cu(II) with the ligand is responsible for the observed high cytotoxicity of the copper(II) complexes and the 1:2 copper species 1 and 2 demonstrate lower antitumor activities than that of the 1:1 copper species 4 and 5. In addition, the in vitro apoptosis inducing activity of the copper(II) complex 5 against SGC7901 cell line is determined. And the results show that the complex can bring about apoptosis of the cancerous cells in vitro.
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•Five copper(II) complexes with different number of metal centers have been synthesized and characterized.•The results indicate that the five copper(II) complexes show good cytotoxicity.•The flow cytometry and western blotting show that complex 5 can bring about apoptosis of tumor cells.
The dark-red title complex crystallized from an equimolar methanol solution of (
E
)-5-(ethylamino)-4-methyl-2-(pyridin-2-yl)diazenylphenol and CuCl
2
(phen) (phen = 1,10-phenanthroline) as a ...centrosymmetric dimer, CuCl(C
14
H
15
N
4
O)
2
. The Cu atoms are bridged by two Cl ligands and have a slightly distorted square-pyramidal coordination, where two N atoms from the azo and the pyridine moieties, a phenolic O and a Cl atom comprise the base and the other Cl occupies the apex position. The apical Cu—Cl bond, 2.6192 (4) Å, is longer than the basal one, 2.2985 (3) Å, due to Jahn–Teller distortion. The dimers are associated
via
weak intermolecular hydrogen bonds and π–π stacking interactions between phenyl and pyridine rings. A monomeric by-product of the same reaction, CuCl(phen)
2
Cl·4H
2
O, has a trigonal–bipyramidal coordination of Cu with equatorial Cl ligand, and extensive outer-sphere disorder. In the structure of
4
, the packing of cations leaves continuous channels containing disordered Cl
−
anions and solvent molecules. The identity of the solvent (water or a water/methanol mixture) was not certain. The disordered anion/solvent regions comprise 28% of the unit-cell volume. The disorder was approximated by five partly occupied positions of the Cl
−
anion and ten positions of O atoms with a total occupancy of 3, giving a total of 48 electrons per asymmetric unit, in agreement with the integral electron density of 47.8 electrons in the disordered region, as was estimated using the BYPASS-type solvent-masking program van der Sluis & Spek (1990).
Acta Cryst.
A
46
, 194–201.
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