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Copper thiocyanate (CuSCN) is known as a promising hole transport layer in organic photovoltaics (OPVs) due to its good hole conduction and exciton blocking abilities with high transparency. Despite its successful device applications, the origin of its hole extraction enhancement in OPVs has not yet been understood. Here, we investigated the electronic structure of CuSCN and the energy level alignment at the poly(3-hexylthiophene-2,5-diyl) (P3HT)/CuSCN/ITO interfaces using ultraviolet photoelectron spectroscopy. The band-tail states of CuSCN close to the Fermi level (EF) were observed at 0.25 eV below the EF, leading to good hole transport. The CuSCN interlayer significantly reduces the hole transport barrier between ITO and P3HT due to its high work function and band-tail states. The barrier reduction leads to enhanced current density-voltage characteristics of hole-dominated devices. These results provide the origin of hole-extraction enhancement by CuSCN and insights for further application.

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

 

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When an electrodeposited CuSCN thin film was inserted into the interface of ITO/P3HT:PCBM blended solid film (P3HT: regioregular poly(3-hexylthiophene), PCBM: soluble [6,6]-phenyl C61 buttyric acid methyl ester) in ITO/P3HT:PCBM/ Al sandwich-type solar cells, the cell performance was remarkably improved, resulting in 2.5% of energy conversion yield under the irradiation of AM 1.5-100 mW/cm2 simulated sunlight. Copyright

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

 

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Two novel cation-induced complexes, {(Phen-dq) [Cu2(SCN) 4]}n (1) and {(Phen-dzp) [Cu2(SCN) 4]}n (2) [Phen-dq = (C14H12N 2)2+, 5,6-dihydropyrazino[1, 2, 3, 4-lmn]-1, 10-phenanthrolinium, Phen-dzp = (C15H14N2) 2+, 6,7-dihydro-5H-[1, 4]diazepino[1, 2, 3, 4-lmn][1,10] phenanthroline-4, 8-diium], have been synthesized via the self-assembly reaction in solution. The compound 1 possesses a two-dimensional supramolecular network linked by bridging thiocyanate groups. Complex 2 is also a two-dimensional polymeric architecture with the organic cation Phen-dzp trapped in it. Each Cu(I) atom is coordinated by two N atoms and two S atoms from four NCS groups to form a Cu2(NCS)2 rectangular dimer unit. In these two compounds, thanks to the difference from organic cations, the simple modification from Phen-dq to Phen-dzp leads to distinct structures between 1 and 2, and these “planar” cations are effective guests to manipulate the aggregate structure of thiocyanatocuprates.

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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 reaction of cis-1,2-bis(diphenylphosphino)ethylene (dppet) with CuX (X = CN, SCN) in 1:1 M molar ratio in DCM-MeOH (50:50 V/V) under refluxing conditions gave two dimeric Cu(i) complexes, viz. [Cu2(mu-CN)2(kappa2-P,P-dppet)2] (1) and [Cu2(mu2-SCN)2(kappa2-P,P-dppet)2] (2). These complexes have been characterized by elemental analyses, IR, 1H and 31P NMR, and electronic absorption spectroscopies, and ESI-MS. The molecular structure of 2 was confirmed by single crystal X-ray diffraction, which indicated that 2 exists as a centrosymmetric dimer in which the two copper centers are bonded to two dppet ligands and two bridging thiocyanate groups in a mu2-manner. The electrochemical properties of 1 and 2 were studied by cyclic voltammetry. Both the complexes exhibited strong luminescence properties in the solution state at ambient temperature. Both the complexes were found to be efficient catalysts for the conversion of terminal alkynes into propiolic acids with CO2. Owing to their excellent catalytic activity, the reactions proceed at atmospheric pressure and ambient temperature (25 C). The catalytic products were obtained in excellent yields (90-97%) by using the complex loading of 1 mol%.

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

 

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One of the most promising among hole-conducting materials, CuSCN, was prepared for the first time in a form of porous layers for potential applications in inverted perovskite solar cells.

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

 

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Nanocrystals of multicomponent chalcogenides, such as Cu 2ZnSnS4 (CZTS), are potential building blocks for low-cost thin-film photovoltaics (PVs). CZTS PV devices with modest efficiencies have been realized through postdeposition annealing at high temperatures in Se vapor. However, little is known about the precise role of Se in the CZTS system. We report the direct solution-phase synthesis and characterization of Cu 2ZnSn(S1-xSex)4 nanocrystals (0 ? x ? 1) with the aim of probing the role of Se incorporation into CZTS. Our results indicate that increasing the amount of Se increases the lattice parameters, slightly decreases the band gap, and most importantly increases the electrical conductivity of the nanocrystals without a need for annealing.

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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 series of stable, coloured and diamagnetic copper(I) azido complexes of the type CuLnN2, where L=3-, and 4-CHO-py, 2-, 3-, and 4-COCH3-py, 2-, 3-, and 4-COOCH3-py, 2-, 3-, and 4-COOC2H5-py, 2-COC6H5-py and 4-CN-py, n=1 or 2, in addition to some new CuL2(NCS) complexes have been isolated and characterized.All these carbonyl ligands act as monodentate ones in the isolated complexes.IR results suggest that the azide groups in the isolated azido complexes act as bridging ligands through the two end nitrogen atoms.CuL2(NCS) complexes have almost distorted tetrahedral geometry through bridging thiocyanate groups.

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

 

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(Chemical Equation Presented) A novel electrophilic ipso-cyclization involving an electrophile-exchange process has been developed. In the presence of CuX (X = I, Br, SCN) and electrophilic fluoride reagents, a variety of N-(p-methoxyaryl)propiolamides and 4-methoxyphenyl 3-phenylpropiolate were cyclized to selectively afford the corresponding spiro[4.5]decenones in moderate to good yields. It is noteworthy that two azaquaternary tricyclic products were synthesized through a two-step pathway involving an electrophilic ipso-cyclization and then an intramolecular Heck reaction.

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

 

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Complexes containing di(2-pyridyl) ketone (dpk) as a bi- (N,N) and tridentate (N,N,O) ligand have been synthesised1,2 and characterized by spectral and structural studies. Products 1 and 2 are polymorphs of the polymeric copper(I) complex [Cu(dpk)(NCS)]n containing dpk with thiocyanate anions which bridge to form a one-dimensional continuous polymer chain. The novel dinuclear copper(II) complex [Cu2(dpkA·acetone) 2(NCS)2] (3) was formed when 1 and 2 were allowed to stand in the supernatant. In this instance it appears that a transition-metal- promoted aldol condensation has occurred between the solvent acetone and the ketone carbonyl of dpk to produce the novel ligand, dpkA·acetone. Product 3 contains two five-coordinate copper(II) ions, both with trigonal bipyramidal coordination, bridged through deprotonated hydroxy groups on each dpkA·acetone. A chemical rationalisation for the formation of 3 is proposed. The dinuclear copper(I) complex [Cu2(dpk)2I 2] (4) is also reported, which contains two four-coordinate copper(I) ions that are bridged together through iodide ions.

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