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Synthesis, characterization, and X-ray crystal structures of copper(I) halide and pseudohalide complexes with 2-(2-quinolyl)benzothiazole. Diverse coordination geometries and electrochemical properties

Three new copper(I) complexes with the ligand 2-(2-quinolyl)benzothiazole (qbtz) have been synthesized and characterized by elemental analyses, infrared, and ultraviolet?visible spectroscopy, and their crystal structures have been determined by X-ray diffraction. The coordination geometry around copper in [Cu(qbtz)(mu-I)]2, complex (1), a centrosymmetric dimer, is a distorted CuI2N2 tetrahedron supplemented by a short Cu?Cu interaction of 2.5855 A. The copper(I) cyanide?bridged complex [Cu3(qbtz)2(mu-CN)3] (2) exhibits a one-dimensional chain structure with three crystallographically independent Cu atoms. Two of the copper atoms feature tetrahedral four coordination each by a chelating qbtz ligand and two CN groups, and the third features a quasi-linear two-coordination geometry by two CN. In [Cu(qbtz)(mu-SCN)] (3), copper is in a distorted tetrahedral coordination by two N atoms of a chelating qbtz ligand and by one N atom and one S atom of a bridging SCN group. The complex exhibits a one-dimensional zigzag chain structure with two crystallographically inequivalent Cu atoms in the chain. The spectroscopic and electrochemical properties of compounds 1?3 are in accord with the variation in copper(I) coordination environments.

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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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Seven copper (I) complexes of diphosphine ligands and N^N ligands: Syntheses, structural characterizations and spectroscopic properties

The reactions of diphosphine ligands and nitrogen-containing ligands with Cu(I) salts in the mixed solvents of methanol (MeOH) and dichloromethane (CH2Cl2) generated the corresponding complexes, {[Cu(dppbe)(Bphen)](ClO4)¡¤2CH3OH}n (1), {[Cu2(dppe)(dmp)2(CN)2]¡¤2CH3OH}n (2), {[Cu2(dppb)(dmp)2I2]¡¤2CH3OH}n (3), [Cu(POP)(C16H6N6)]I (4), {[Cu(POP)(C16H6N6)](SCN)}n (5), [Cu(xantphos)(bpy)](ClO4) (6) and {[Cu(xantphos)(bpy)](CF3SO3)}n (7) {dppbe = 1,2-bis(diphenylphosphanyl)benzene, dppe = 1,2-bis(diphenylphosphino)ethane; dppb = 1,4-bis(diphenylphosphino)butane, POP = bis[2-(diphenylphosphino)phenyl]ether, xantphos = 4,5-bis (diphenylphosphio)-9,9-dimethylxanthene, Bphen = 4,7-diphenyl-1,10-phenanthroline, dmp = 2,9-dimethyl-1,10-phenanthroline, C16H6N6 = [2,3-f]-pyrazino-[1,10]phenanthroline-2,3-dicarbonitrile, bpy = 2,2?-bipyridine}. These complexes were all characterized by single-crystal X-ray crystallography, elemental analysis, IR, 1H NMR spectroscopy, luminescence and THz spectroscopy. Complexes 1 and 2 consist of 1D infinite zigzag chain structures which are linked by hydrogen bonds, while complexes 3, 5 and 7 have 2D topological architectures which are connected by hydrogen bonds, complex 4 has an annular structure and complex 6 is a mononuclear structure. The types of hydrogen bonds, choice of solvents and coordination modes of the ligands are of importance in defining the structural and topological features of the resulting networks. Furthermore, complexes 1?7 exhibit interesting luminescence in the solid state at room temperature. Complexes 1?3 can act as yellow luminophores, complex 4 acts as a red luminophore, complex 5 acts as an orange luminophore and complexes 6?7 act as green luminophores. Their terahertz spectra show more accurate characteristics of their structures.

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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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REACTION OF OLEFINS WITH A MIXTURE OF IODINE AND MERCURY(II) THIOCYANATE. PREDOMINANT FORMATION OF vic-IODO(ISOTHIOCYANATO)ALKANES.

Treatment of olefins with a mixture of iodine and mercury(II) thiocyanate in benzene or diethyl ether gives vic-iodo(isothiocyanato)alkanes and vic-iodo(thiocyanato)alkanes in a high yield, the former being predominant. Similar results were obtained by using silver(I) and thallium(I) thiocyanates, though both the yield and the selectivity are slightly lower. By use of potassium thiocyanate and copper(I) isothiocyanate in place of mercury(II) thiocyanate, beta -iodo thiocyanates were mainly formed. A reaction scheme involving initial formation of an iodonium ion from olefin and ISCN (formed in situ) and a subsequent attack of complex anion I(SCN)//2** minus has been proposed to account for this predominant formation of beta -iodo isothiocyanates.

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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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Investigation of structure-directing interactions within copper(i) thiocyanate complexes through X-ray analyses and non-covalent interaction (NCI) theoretical approach

Herein, we reported the synthesis of copper(i) thiocyanate complexes with ortho-pyridinyl carbohydrazones containing a thiophene (L1) or a furyl ring (L2) as a mixture of two different crystals for each compound, linkage isomers of C1N, [Cu(NCS)(L1)PPh3] and C1S, [Cu(SCN)(L1)PPh3], for L1, whereas monomeric and polymeric structures C2N, [Cu(NCS)(L2)PPh3], and C2P, [-(NCS)Cu(L2)-]n, for L2. Crystallographic information and theoretical calculations, mainly noncovalent interaction reduced density gradient (NCI-RDG) analyses, were pursued to generate a profound understanding of the structure-directing interactions in these complexes. The supramolecular assemblies are first driven by cooperative pi?pi interactions and hydrogen bonds followed by CH?pi, S?S and S?pi linkages. In the case of the linkage isomers, intermolecular interactions may have a significant role in the formation of the less stable S-bound isomer C1S.

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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 halide clusters and polymers supported by bipodal heteroelemental ligands

The flexible, multi dentate, heteroelemental, dipodal ligands; bis(2pyridylthio)methane, (PyS)2CH2 (Py = pyridyl = C5H4N), (PymS)2CH2, bis(2pyrimidylthio)methane, and bipyrimidyldisulfide, (PymS)2 (Pym = pyrimidine, C4H3N2), were reacted with a series of copper precursors to determine whether monomeric compounds, cubane clusters or polymeric chains would be obtained. Copper(II) chloride, copper(I) cyanide and copper(I) thiocyanate afforded infinite polymeric chains while copper(I) iodide afforded tetranuclear clusters supported by two ligand molecules. All products were characterized in the solid-state by X-ray crystallography.

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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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Tuning chemistry of CuSCN to enhance the performance of TiO 2/N719/CuSCN all-solid-state dye-sensitized solar cell

CuSCN with enhanced p-type conductivity was prepared by replacing some of the cuprous sites by triethylamine coordinated Cu(i) with concomitant (SCN) 2 doping to introduce more holes. A compound Cu5[(C 2H5)3N]3(SCN)11 was isolated and well characterized. A 41% enhancement of energy conversion efficiency of the TiO2/N719/modified CuSCN cell from the best reported value and more than a factor of ten from bare CuSCN was achieved.

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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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Aqueous phase self-assembly of nanoscale p-n heterojunctions

Methods, adapted from photographic microcrystal growth technology, are used to assemble organized ternary organo-inorganic, nanoscale heterostructures. The resulting ensemble consists of free-standing, oriented AgBr microcrystals, upon the a??111a?? surfaces of which is self-assembled a monolayer of spectrally sensitizing dye, and upon the corners of the hexagonally shaped AgBr substrates are epitaxially grown nanoscale p-type CuSCN nodules. EPR spectroscopy and photophysical measurements are employed to show that the ensembles are capable of separating photogenerated geminate pairs. One of the remarkable features of this approach is that it utilizes the ultrafast kinetics of aqueous precipitation and, thus, allows the assembly of heterostructures at rates of 1010/sA¡¤L, or greater.

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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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Corrosion and fouling study of copper-based antifouling coatings on 5083 aluminum alloy

Potentiostatic and electrochemical impedance spectroscopy (EIS) were used to evaluate cuprous oxide (Cu2O) containing coating systems on the localized corrosion of 5083 marine-grade aluminum in simulated ocean water. Test panels coated with a complete coating system and flawed to simulate a coating defect were also exposed for a 3-month field immersion to evaluate differences between Cu2O and cuprous thiocyanate (CuSCN) pigments on fouling and corrosion behaviour. Optical microscopy, scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDS) were used to evaluate deposits formed on the surfaces after exposure. Results imply that copper leaching from the Cu2O pigment can deposit on the surface marine-grade aluminum, with or without cathodic protection. Cathodic protection resulted in the formation of protective calcareous deposits at potentials more electronegative than ?1000 mV versus silver-silver chloride (Ag/AgCl). Cuprous oxide was shown to be a more resistant to biofouling than the cuprous thiocyanate, but there was an increased likelihood of coating delamination and localized corrosion with the former antifouling pigment.

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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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Charge Transport and Recombination in a Nanoscale Interpenetrating Network of n-Type and p-Type Semiconductors: Transient Photocurrent and Photovoltage Studies of TiO2/ Dye/CuSCN Photovoltaic Cells

Solid-state dye-sensitized photovoltaic cells have been fabricated with TiO2 as the electron conductor and CuSCN as the hole conductor. These cells involve the nanoscale mixing of crystalline n-type and p-type semiconductors in films that are more than 100 times thicker than the individual n- and p-type domains. Charge transport and field distribution in this kind of material are as yet unexplored. We have used photocurrent and photovoltage transients, combined with variation in the layer thickness, to examine the limiting factors in charge transport and recombination. Charge transport (t 1/2 a?? 200 I?s) is found to be similar to that in dye-sensitized electrolyte cells. Recombination at Voc (t1/2 a?? 150 I?s) is 10 times faster than in electrolyte cells, and recombination at short circuit (t1/2 a?? 450 I?s) is 100 times faster. In the solid-state cells, the similarity of the charge transport and recombination rates results in a low fill factor, and photocurrent losses, both important limiting factors of the efficiency. A simple model is given, and suggestions are made for improvements in efficiency.

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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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Process for the synthesis of azobenzene compounds having a cyano group in one or both of the ortho positions of the diazo component radical

A process for the synthesis of an azobenzene compound having a cyano group in one or both of the ortho positions of the diazo component radical comprising reacting the corresponding azobenzene compound having a chloro, bromo or iodo substituent in one or both of the ortho positions of the diazo component radical with a copper thiocyanate or copper thiocyanate-forming mixture of salts in the presence of an oxidizing agent (e.g., oxygen and sodium perborate), whereby the or at least one of the chloro, bromo and iodo substituents is replaced by a cyano group.

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