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Abstract: Nanostructured inorganic?organic hybrid thin films of copper(I) thiocyanate (CuSCN) and 4-(N,N-dimethylamino)-4?-(N?-methyl)stilbazolium tosylate (DAST) were electrochemically self-assembled by adding DAST into methanolic bath containing Cu2+ and SCN? ions. Loading of the stilbazolium organic chromophore (DAS+) increased linearly on increasing DAST concentration, accompanied with changes of the film morphology, crystallographic orientation of CuSCN and transition from beta- to alpha-CuSCN. At low DAST concentrations, transport limited passive occlusion of DAS+ has been suggested with its diffusion coefficient of 1.25 × 10?6 cm2 s?1 in methanol at 298 K, while the loading receives kinetic limitation by the surface chemical reaction to yield definitive hybrid structures, resulting in unique ?hair comb? shape beta-CuSCN-DAST and ?nano-platelets? shape alpha-CuSCN-DAST hybrid structures. Both the inorganic and organic components are interconnected and bi-continuous, as the loaded DAS+ could be totally extracted by dimethylacetamide to leave porous skeleton of crystalline CuSCN, making them highly interesting for device applications. Graphical abstract: [Figure not available: see fulltext.]

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

 

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This study focuses on employing cuprous iodide (CuI) as a hole-transporting material (HTM) in fabricating highly efficient perovskite solar cells (PSCs). The PSCs were made in air with either CuI or 2,2′,7,7′-Tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9′-spirobifluorene (spiro-OMeTAD) as HTMs. A simple and novel pressing method was employed for incorporating CuI powder layer between perovskite layer and Pt top-contact to fabricate devices with CuI, while spiro-OMeTAD was spin-coated between perovskite layer and thermally evaporated Au top-contact to fabricate devices with spiro-OMeTAD. Under illuminations of 100 mW/cm2 with an air mass (AM) 1.5 filter in air, the average short-circuit current density (JSC) of the CuI devices was over 24 mA/cm2, which is marginally higher than that of spiro-OMeTAD devices. Higher JSC of the CuI devices can be attributed to high hole-mobility of CuI that minimizes the electron-hole recombination. However, the average power conversion efficiency (PCE) of the CuI devices were lower than that of spiro-OMeTAD devices due to slightly lower open-circuit voltage (VOC) and fill factor (FF). This is probably due to surface roughness of CuI powder. However, optimized devices with solvent-free powder pressed CuI as HTM show a promising efficiency of over 8.0 % under illuminations of 1 sun (100 mW/cm2) with an air mass 1.5 filter in air, which is the highest among the reported efficiency values for PSCs fabricated in an open environment with CuI as HTM.

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

 

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We show herein that the photoelectrochemical behavior of a given semiconductor nanodot (p-CuSCN or n-TiO2) in an alumina template matrix, is remarkably different than that of its macro-sized counterpart. Three separate examples of this distinct difference in behavior are presented. It is shown how the photoresponse (e.g. photocurrent) may be amplified (from a low level typical of the signal emanating from a ?10-11 cm2 region corresponding to a semiconductor nanodot) by using a large number of electrically inter-connected Au nanowires to support the overlying semiconductor nanodots. The anomalous photoresponse of p-CuSCN nanodots in the template matrix was also numerically simulated by a simple parallel equivalent circuit consisting of a semiconductor and a photocapacitor. Possible practical application scenarios are finally presented for these nanostructures.

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

 

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(Figure Presented) All wrapped up: Supramolecular polymeric helices were fabricated by using cluster helicates as templates. The helicity of the template (see picture; gold spheres: Ni or Zn; blue spheres: O), upon hydrothermal treatment with CuSCN (gray spheres), is transferred to the strands of the resulting copper-based coordination polymer, which is wrapped around the helicate units in the final product.

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

 

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The hydro/solvothermal reactions of Cu(I)/Cu(II) salt, NaN3, and acetonitrile in water or methanol yield two noninterpenetrated supramolecular networks containing 1D hexagonal and square nanochannels, {[Cu(Mtta)]·0.17H2O}n (1) and its pseudopolymorph [Cu(Mtta)]n (2) (Mtta = 5-methyl tetrazolate), involving ligand insitu formation by cycloaddition of nitriles and azides. The copper-(I) centers in both complexes are all bridged by Mtta ligands, forming the different shapes of the cavity. 1 exhibits an unprecedented uniform (8, 3) topological metal network, whereas 2 is a 3-connected (8210) metal net.

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

 

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A method has been developed for the synthesis of alpha-trifluoromethyl ketones via the Cu-catalyzed trifluoromethylation of silyl enol ethers with an electrophilic trifluoromethylating agent, which produces a trifluoromethyl radical.

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

 

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

 

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Syntheses, spectroscopic characterization and single crystal X-ray studies are reported for a number of complexes of copper(II) salts with simple monodentate nitrogen bases. The 1:4 adduct of copper(II) sulfate with 3,5-dimethylpyridine (m2py) CuSO4·4m2py, takes the form [(O3SO)Cu(m2py)4], the Cu-O vector of the square-pyramidal coordination environment being disposed on the 4-axis in tetragonal space group P4/n. The complex CuCO3· Cu(NCS)2·4py is a linear polymer, taking the form ?O·Cu(py)2·O·C{O·Cu(py) 2(NCS)2}·O·Cu(py)2? (etc.), all atoms lying in the mirror plane of space group Pnma, excepting the pair of ‘py’ (pyridine) ligands disposed to either side. In Cu(OH)I·3/ 4I2·2py·1/2MeCN ? [{(py)2Cu(OH)} 4](I3)3I·2MeCN a novel cubanoid tetranuclear cation is found (2-symmetry). The EPR spectra of the above compounds show a trend in the anisotropy of the g-values that correlates well with the crystal structures. Obtained only in small quantities but supported by single crystal X-ray studies are the adduct of Cu(OH)Cl with pyrrolidine (pyrr), Cu(OH)Cl:pyrr (1:3), which takes the centrosymmetric binuclear form [(pyrr)3Cu(mu-OH)2Cu(pyrr)3]Cl2, the copper atom being disposed in a distorted trigonal bipyramidal array, and the adduct 3CuCl2·CuO·4quin, [Cu4Cl 6O(quin)4]Cl2, which contains the familiar Cu4Cl6O core with monodentate quinuclidine (quin) attached to the copper atoms; this compound crystallizes in the cubic space group 4?3m.

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

 

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In classical electrochemical theory, both the electron transfer rate and the adsorption of reactants at the electrode control the electrochemical reaction. COA of Formula: CCuNS. Introducing a new discovery about 1111-67-7, Name is Cuprous thiocyanate

A family of brightly luminescent dinuclear complexes of [Cu(mu2-X)(N^N)]2 type (X = I or SCN) has been synthesized in 76-90% yields by the reaction of bis(2-pyridyl)phosphine oxides (N^N) with the corresponding Cu(i) salts. The X-ray diffraction study reveals that the Cu2I2 core of the [Cu(mu2-I)(N^N)]2 complexes has either a butterfly- or rhomboid-shaped structure, while the eighth-membered [Cu(SCNNCS)Cu] ring in the [Cu2(SCN)2(N^N)]2 complexes is nearly planar. In the solid state, these compounds exhibit a strong green-to-yellow emission (lambdaemmax = 536-592 nm) with high PLQYs (up to 63%) and short lifetimes (1.9-10.0 mus). The combined photophysical and DFT study indicates that the ambient-temperature emission of the complexes obtained can be assigned to the thermally activated-delayed fluorescence (TADF) from the 1(M + X)LCT excited state, while at 77 K, phosphorescence from the 3(M + X)LCT state is likely observed.

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

 

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Seven conductive radical cation salts based on MDSe-TSF (methylenediselenotetraselenafulvalene) have been synthesized by electrocrystallization in the presence of Cl-, Br-, I3-, I2Br-, PF6-, ClO4-, and Cu(NCS)2- counter anions. The crystal appearances of these salts fairly depend on the anions employed. X-ray crystallographic analyses have revealed that the PF6 and ClO4 salts in the shape of brown thin plates adopt the theta-type structures characterized by the herringbone arrangement of donor stacks, whereas the Cl and Br salts in the shape of black thick plates favor the kappa-type structures with the orthogonal arrangement of donor dimers. Regardless of different crystal appearances or crystal packing patterns, all these salts show high conductivity (> 102 S cm-1) at room temperature and retain metallic properties down to 4.2 K. Of them, the Br salt shows a weak but distinct diamagnetic shielding signal below 4 K in the dc magnetization measurement under zero-field-cooled (ZFC) condition, suggesting a sign of superconductivity. The band calculations of both PF6 and Br salts demonstrate closed Fermi surfaces indicative of two-dimensional molecular conductors.

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