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Synthesis, spectral studies of cobalt(II) tetrathiocyanoto dicuperate(I) complexes with some acylhydrazones and their antimicrobial activity

Cobalt(II) complexes of the type Co[Cu(NCS)2]2 ? L, where L is acetophenonebenzoylhydrazone (Abh), acetophenoneisonicotinoylhydrazone (Ainh), acetophenonesalicyloylhydrazone (Ash), acetophenoneanthraniloylhydrazone (Aah), p- hydroxyacetophenonebenzoylhydrazone (Phabh), p- hydroxyacetophenoneisonicotinoylhydrazone (Phainh), p- hydroxyacetophenonesalicyloylhydrazone (Phash), and p- hydroxyacetophenoneanthraniloylhydrazone (Phaah) were synthesized and characterized by elemental analyses, molar conductance, magnetic moments, electronic and IR spectra, and X-ray diffraction studies. The complexes are insoluble in common organic solvents and are non-electrolytes. These complexes are coordinated through the >C=O and >C=N groups of the hydrazone ligands. The magnetic moments and electronic spectra suggest a spin-free octahedral geometry around Co(II). The X-ray diffraction parameters (a, b, c) for Co[Cu(SCN)2]2 ? Ainh and Co[Cu(SCN)2] 2 ? Phabh correspond to orthorhombic and tetragonal crystal lattices, respectively. The complexes show a fair antifungal and antibacterial activity against a number of fungi and bacteria. The activity increases with increasing concentration of the compounds.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Development of Sensor Based on Copper(II) Thiocyanate Pyridine Polymeric Complex for Detection of Catechol

The reaction of copper(I) thiocyanate with triphenylphosphine, in pyridine, in air and at room temperature, led to the formation of the copper(II) thiocyanate pyridine polymeric complex [Cu2(mu3 CO3)(NCS)2(Py)4]n in the form of deep blue needle-like crystals. Fourier transform infrared spectroscopy (FTIR), elemental analysis (EA), thermogravimetric analysis (TGA) and single crystal X-ray diffraction analysis (XRD) were performed in order to reveal the identity of the obtained complex. The complex is a coordination polymer that crystallizes in the orthorhombic space group Pnma and has a one-dimensional linear structure running along the crystallographic ${a}$ axis. Here, we report the investigation of the electrochemical properties of this polymeric compound, collected in acetonitrile solution and KClO4 as electrolyte, by cyclic voltammetry and square wave voltammetry. The voltammograms showed four peak pairs related to redox processes of copper ion and electroactive ligands. Moreover, we used this compound as modifier of carbon paste electrodes, whose electrochemical properties were studied in different electrolytes and electrochemical redox probes. These studies demonstrate the valuable electrochemical and electrocatalytic properties of the [Cu2(mu3 -CO3)(NCS)2(Py)4]npolymerimmobilized in the carbonaceous matrix. The sensor developed by using the carbon paste method has shown excellent sensitivity for catechol, good repeatability, selectivity, stability, and applicability in detection of catechol in water samples.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Electrochemical deposition characteristics of p-CuSCN on n-ZnO rod arrays films

p-CuSCN/n-ZnO rod array heterojunctions were electrodeposited with a weak basic (pH ?9) aqueous electrolyte solution. I-V characteristics showed the heterostructure had clear rectification, indicating good electrical contacts between ZnO rod arrays and the embedded CuSCN. The energy band model for the electrodeposition of CuSCN on ZnO rod arrays was proposed based on linear sweep voltammetric (LSV) measurements, which indicated that the electrodeposition process was the prior growth of CuSCN on bare ZnO rods according to a conduction process, followed by compact filling in the gaps of the arrays based on the thermal activation mechanism of surface states. The diode properties of the heterojunctions revealed that although deposition was dominated by thermal activation mechanism of surface states, the electrodeposition should be performed at a lower temperature in order to reach fine filling of the gaps of ZnO rod arrays.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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A novel two-dimensional CuSCN network templated by 2,2?-dimethyl-1, 1?-(butane-1,4-diyl)bis(1H-imidazol-3-ium) cations

The cation-templated self-assembly of 1,4-bis(2-methyl-1Himidazol-1-yl) butane (bmimb) with CuSCN gives rise to a novel two-dimensional network, namely catena-poly[2,2?-dimethyl-1,1?-(butane-1,4-diyl)bis(1H-imidazol-3- ium) [tetra-mu2-thiocyanato-kappa4S: S;kappa4S:N-dicopper(I)]], {(C12H20N 4)[Cu2-(NCS)4]}n. The CuI cation is four-coordinated by one N and three S atoms, giving a tetrahedral geometry. One of the two crystallographically independent SCN- anions acts as a mu2-S:S bridge, binding a pair of CuI cations into a centrosymmetric [Cu2(NCS)2] subunit, which is further extended into a twodimensional 44-sql net by another kind of SCN – anion with an end-to-end mu2-S:N coordination mode. Interestingly, each H2bmimb dication, lying on an inversion centre, threads through one of the windows of the two-dimensional 44-sql net, giving a pseudorotaxane-like structure. The two-dimensional 44-sql networks are packed into the resultant three-dimensional supramolecular framework through bmimb-SCN N-H…N hydrogen bonds.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Copper-catalyzed intramolecular C(sp3)-H and C(sp2)-H amidation by oxidative cyclization

The first copper-catalyzed intramolecular C(sp3)-H and C(sp 2)-H oxidative amidation has been developed. Using a Cu(OAc) 2 catalyst and an Ag2CO3 oxidant in dichloroethane solvent, C(sp3)-H amidation proceeded at a terminal methyl group, as well as at the internal benzylic position of an alkyl chain. This reaction has a broad substrate scope, and various beta-lactams were obtained in excellent yield, even on gram scale. Use of CuCl2 and Ag2CO3 under an O2 atmosphere in dimethyl sulfoxide, however, leads to 2-indolinone selectively by C(sp2)-H amidation. Kinetic isotope effect (KIE) studies indicated that C-H bond activation is the rate-determining step. The 5-methoxyquinolyl directing group could be removed by oxidation. Silver ox: By using a Cu(OAc)2 catalyst and an Ag2CO3 oxidant in dichloroethane solvent, C(sp3)-H amidation proceeded at a terminal methyl group as well as at the internal benzylic position of an alkyl chain. This reaction has a broad substrate scope, and various beta-lactams were obtained in excellent yield, even on a gram scale. Use of CuCl2 and Ag2CO3 under an O2 atmosphere led to 2-indolinone selectively synthesized by C(sp2)-H amidation. DMSO=dimethylsulfoxide.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Novel 2D material from AMQS-based defect engineering for efficient and stable organic solar cells

In this work, soluble two-dimensional (2D) material of antimonene quantum sheets (AMQSs) is used to form a bilayer hole extraction layer (HEL) with CuSCN. It proves that the application of AMQSs helps to passivate surface defects of CuSCN, resulting in diminished recombination loss and depressed exciton quenching effect, and thereby achieving improved photovoltaic performance. In OPVs based on poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b;4,5-b?]dithiophene-2,6-diyl-alt-(4-(2-ethylhexyl)-3-fluorothieno[3,4-b]thiophene-)-2-carboxylate-2-6-diyl)]: [6,6]-phenyl C71-butyric acid methyl ester (PTB7-Th:PC71BM), over 12% enhancement of power conversion efficiency (PCE) is observed compared to that of the reference cell fabricated with pure CuSCN as an HEL. The advantage of the bilayer CuSCN/AMQS HEL is also confirmed in non-fullerene systems of PBDB-T-2F:IT-4F and PTB7-Th:ITIC. In a cell based on PBDB-T-2F:IT-4F, a PCE of 10.14% was obtained after application of AMQSs, which improved by about 10% compared to that of the reference cell using pure CuSCN as an HEL. Furthermore, cells based on CuSCN and CuSCN/AMQS HEL exhibit superior air stability. The use of a bilayer CuSCN/AMQS HEL provides a promising approach to obtain efficient and stable organic solar cells.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Structural studies on tris(2-cyanoethyl)phosphine complexes of Cu(I): The sensitivity of the secondary nitrile coordination to the nature of the anion

Tris(2-cyanoethyl)phosphine (tcep) reacts with the copper(I) compounds, CuX (X = Cl, Br, I and SCN), in a 1:1 ratio to give 1:1 complexes, CuX(tcep), whereas it reacts with CuY (Y = PF6, ClO4, NO3, BH4, CN and CF3COO) in a 2:1 ratio to give the 2:1 complexes, CuY(tcep)2. Single crystal X-ray structures show that for the anions X = Br and SCN, the complexes are coordination polymers, [CuX(tcep)]n, with the Cu centres being bridged by the anion, and as well, one nitrile arm per tcep ligand coordinates intermolecularly to the Cu to give tetrahedral ‘PBr2N’ and ‘PSN2’ coordination spheres respectively. The 2:1 compounds exhibit a variety of structures. For Y = ClO4, CN and CF3COO polymeric structures are formed except for Y = BH4 where the compound is a discrete monomer, [Cu(BH 4)(tcep)2], with a chelating anion and two monodentate P-bound tcep ligands. Both the compounds obtained with Y = CN and CF 3COO also contain coordinated anions and are formulated as [Cu(CN)(tcep)2]n and [Cu(CF3COO)(tcep) 2]n respectively. In the case of Y = CN the anion is bridging and the tcep ligands are only P-bound giving a ‘P2NC’ coordination sphere. In contrast, for Y = CF3COO, the anion is an O-bound monodentate and the tcep ligands bridge to give a ‘P2NO’ environment for the copper. In the case of Y = ClO4, the anion is not coordinated but a polymeric structure, [Cu(tcep)2] n(ClO4)n, is formed via bridging tcep ligands linking Cu centres intermolecularly resulting in a ‘P2N2’ coordination sphere.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Improving the efficiency and stability of inverted perovskite solar cells by CuSCN-doped PEDOT:PSS

Hole transport layer (HTL) is important in inverted perovskite solar cells (PSCs) to facilitate the hole extraction and suppress the charge recombination for high device performance. Based on the widely used HTL material of poly(ethylenedioxythiophene) (PEDOT):poly(styrenesulfonate) (PSS), we proposed a new HTL modification method using the widely available copper(I) thiocyanate (CuSCN); the doping of CuSCN NH3 [aq] in PEDOT:PSS followed by low-temperature annealing results in reduced energy barrier, improved charge extraction efficiency and increased the mean size of perovskite crystal of the PEDOT:PSS-CuSCN HTL-based inverted PSCs. Significantly improved device performance was observed with open current voltage over 1.0 V and power conversion efficiency (PCE) up to 15.3%, which is 16% higher in PCE than that of the PEDOT:PSS-based PSCs. More impressively, with a lower acidity than PEDOT:PSS, the PEDOT:PSS-CuSCN HTL enables excellent long-term stability of the inverted PSCs, exhibiting almost doubly improved device stability at the same storage condition. Thus, the successful application of CuSCN doping in PEDOT:PSS HTLs should provide a novel approach for the development of high-performance HTLs for highly efficient and stable PSCs.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Thiocyanate hydrometallurgy for the recovery of gold.: Part II: The leaching kinetics

Acid thiocyanate leaching of gold was investigated in the presence of ferric sulfate as an oxidant. According to leaching kinetic studies the initial rate of gold leaching is slow, and not significantly dependent on thiocyanate (0.05-0.2 M) and ferric (0.1-1.0 g/L) concentrations. Ferrous and cupric ions had no effect on leaching kinetics under the conditions studied. In contrast, silver (I) and copper (I) ions significantly impeded the rate of gold leaching. The electrochemical experiments (linear sweep voltammetry and chronoamperometry) indicated that the anodic reaction for gold leaching in acid thiocyanate solutions is the limiting step for the leaching process. Gold dissolution and thiocyanate oxidation participate simultaneously in the anodic process. The addition of thiourea noticeably enhanced the rate of gold leaching. Fourier transform infrared spectroscopy (FTIR) studies demonstrated that thiocyanate and its complexes with the metal ions involved in the leaching systems (Fe (III), Cu (II), Cu (I) and Ag (I)) had very weak adsorption properties at the gold surface.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Synthesis, spectroscopic and structural characterization of adducts of stoichiometry CuX:dppe (1:2) (X = I, ClO4, BH4, O 3SCF3, SCN, dppe = Ph2P(CH2) 2PPh2)

Syntheses and spectroscopic features (IR, NMR and ESI MS) are reported for five 1:2 adducts of CuX with dppe (X = I, ClO4, NCS, O 3SCF3 (tfs) BH4; dppe = Ph2P(CH 2)2PPh2). ESI MS and 31P NMR spectroscopy indicate that these species dissociate in solution yielding free diphosphine and 3:2 species. A single crystal X-ray structure determination has been carried out on Cu(dppe)2NCS defining a four-coordinate complex of the form [(P,P?-dpex)M(P-dpex)X] for M = Cu, the thiocyanate being N-bound; the ionic [Cu(P,P?-dppe)2]tfs has also been structurally characterized.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”