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Copper (I) Selenocyanate (CuSeCN) as a Novel Hole-Transport Layer for Transistors, Organic Solar Cells, and Light-Emitting Diodes

The synthesis and characterization of copper (I) selenocyanate (CuSeCN) and its application as a solution-processable hole-transport layer (HTL) material in transistors, organic light-emitting diodes, and solar cells are reported. Density-functional theory calculations combined with X-ray photoelectron spectroscopy are used to elucidate the electronic band structure, density of states, and microstructure of CuSeCN. Solution-processed layers are found to be nanocrystalline and optically transparent (>94%), due to the large bandgap of ?3.1 eV, with a valence band maximum located at ?5.1 eV. Hole-transport analysis performed using field-effect measurements confirms the p-type character of CuSeCN yielding a hole mobility of 0.002 cm2 V?1 s?1. When CuSeCN is incorporated as the HTL material in organic light-emitting diodes and organic solar cells, the resulting devices exhibit comparable or improved performance to control devices based on commercially available poly(3,4-ethylenedioxythiophene):polystyrene sulfonate as the HTL. This is the first report on the semiconducting character of CuSeCN and it highlights the tremendous potential for further developments in the area of metal pseudohalides.

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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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Mixed-valence CuIICuI15I17 cluster builds up a 3D metal-organic framework with paramagnetic and thermochromic characteristics

Four cubane-like CU4I4 units are assembled around an iodine atom to form the giant, mixed-valent CuIICuI 15I17 cluster. The CuIICuI 15I17 cluster and a bipyrazole linker form a 3D open framework with paramagnetic and thermochromic properties. This paper also touches on the resemblance of this cluster to the self-similar object of a Sierpinski tetrahedron.

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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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Substituted 2-benzothiazolamines as sodium flux inhibitors: Quantitative structure-activity relationships and anticonvulsant activity

Thirty-two aryl-substituted 2-benzothiazolamines have been tested for their ability to modulate sodium flux in rat cortical slices. A QSAR analysis, applied to these derivatives, showed a trend toward increasing potency as sodium flux inhibitors with increasing lipophilicity, decreasing size, and increasing electron withdrawal of the benzo ring substitutents. Additionally, 4- or 5-substitution of the benzo ring was found to decrease potency. The combination of increased lipophilicity, small size, and electron withdrawal severely limited which groups were tolerated on the benzo ring, thus suggesting that the optimal substitution patterns have been prepared within this series. Nine of these compounds were potent inhibitors of veratridine-induced sodium flux (NaFl). These nine compounds also proved to be anticonvulsant in the maximal electroshock (MES) assay. Fourteen additional 2-benzothiazolamines demonstrated activity in the MES screen, yet exhibited no activity in the NaFl assay. These derivatives may be interacting at the sodium channel in a manner not discernible by the flux paradigm, or they may be acting by an alternative mechanism in vivo.

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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 of alpha-trifluoromethyl ketones via the Cu-catalyzed trifluoromethylation of silyl enol ethers using an electrophilic trifluoromethylating agent

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

 

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Novel mixed-metal-alkynyl complexes stabilised by di-imine ligands: Synthesis, characterisation and electrochemistry of [(tBu2bipy)Pt(C?CR)2M(SCN)] (R = C6H4Me, SiMe3; M = Cu, Ag)

Reaction of (4,4?-bis-tert-butyl-2,2?-dipyridyl) platinum bis-alkynyl [(tBu2bipy)Pt(C?CR)2] (R = C6H4Me 1a, SiMe3 1b) with Group 11 metal thiocyanate salts (M = Cu, Ag) affords 1:1 mixed-metal complexes [(tBu2bipy)Pt(C?CR)2M(SCN)] (M = Cu, R = C6H4Me 2a, SiMe3 2b; M = Ag, R = C6H4Me 3a, SiMe3 3b). X-ray analyses of the complexes 2a and 3b show that the group 11 metal is bonded in an eta2 fashion to two carbon-carbon triple bonds so that the co-ordination geometry is trigonal planar. The Pt atom geometry in both complexes is square planar. An electrochemical study of the copper complexes 2a and 2b reveals one fully reversible one electron reduction that is consistent with the first reduction of the co-ordinated bipyridyl ligand. There is also an irreversible one electron oxidation that corresponds to the CuI to CuII transition.

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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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Chelating and bridging bis(diphenylphosphino)aniline complexes of copper(I)

The ligand bis(diphenylphosphino)aniline (dppan) has been shown to be a versatile ligand sporting different coordination modes and geometries as dictated by copper(I) and the counter ion. The molecular structures of its Cu(I) complexes were characterized by X-ray crystallography. The ligand was found in a chelating mode and monomeric complexes were formed when the ligand to copper ratio was 2:1 and the anion was non-coordinating. However, with thiocyanate as the counter anion, the ligand was found to adopt two different modes, with one ligand chelating and the other acting as a monodentate ligand. With CuX (X = Cl, Br), dppan formed a tetrameric complex when the ligand and metal were reacted in the ratio of 1:1. But reactions containing ligand and metal in the ratios of 1:2 or 2:1, resulted in the formation of a mixture of species in solution. Crystallization however, led to the isolation of the tetrameric complex. Variable temperature 31P{1H} NMR spectra of the isolated tetramers did not show the presence of chelated structures in solution. Tetra-alkylammonium salts were added to solutions of various complexes of dppan and studied by 31P{1H} NMR to probe the effect of anions on the stability of complexes in solution. The Cu-dppan complexes were robust and did not interconvert with other structures in solution unlike the bis(diphenylphosphino)isopropylamine complexes.

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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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Two novel nanoporous supramolecular architectures based on copper(I) coordination polymers with uniform (8, 3) and (8210) nets: In situ formation of tetrazolate ligands

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

 

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Sandmeyer difluoromethylation of (hetero-)arenediazonium salts

A Sandmeyer-type difluoromethylation process has been developed that allows the straightforward conversion of (hetero-)arenediazonium salts into the corresponding difluoromethyl (hetero-)arenes under mild conditions. The actual difluoromethylating reagent, a difluoromethyl-copper complex, is formed in situ from copper thiocyanate and TMS-CF2H. The diazonium salts are either preformed or generated in situ from broadly available aromatic amines.

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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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Ligand-controlled mixed-valence copper rectangular grid-type coordination polymers based on pyridylterpyridine

Six mixed-valence CuICuII compounds containing 4?-(4-pyridyl)-2,2?:6?,2?-terpyridine (L1) or 4?-(2-pyridyl)-2,2?:6?,2?-terpyridine (L2) were prepared under the hydrothermal and ambient conditions, and their crystal structures were determined by single-crystal X-ray diffraction. Selection of CuCl 2¡¤2H2O or Cu(CH3COO)2¡¤ H2O with the L1 ligand and NH4SCN, KI, or KBr under hydrothermal conditions afforded 1-dimensional mixed-valence Cu ICuII compounds [Cu2(L1)(mu-1,1-SCN)(mu-Cl) Cl]n (1), [Cu2(L1)(mu-l)2Cl]n (2), [Cu2(L1)(mu-Br)2Br]n (3), and [Cu 2(L1)(mu-1,3-SCN)2(SCN)]n (4), respectively. Compound 5, prepared by layering with CuSCN and L1, is a 2-dimensional bilayer structure. In compounds 1-5, the L1 ligand and X (X = Cl, Br, I, SCN) linked between monovalent and divalent copper atoms resulting in the formation of mixed-valence rectangular grid-type M4L4 or M 6L6 building blocks, which were further linked by X (X = Cl, Br, I, SCN) to form 1- or 2-dimensional polymers. The sizes of M 4L4 units in 1-4 were fine-tuned by the sizes of X linkers. Reaction of Cu(CH3COO)2¡¤H2O with L2 and NH4SCN under hydrothermal conditions gave mixed-valence CuICuII compound [Cu2(L2)(mu-1,3-SCN) 3]n (6). Unlike those in 1-5, the structure of 6 was constructed from thiocyanate groups and the pendant pyridine of L2 left uncoordinated. The temperature-dependent magnetic susceptibility studies on compounds 1 and 4 showed the presence of mixed-valence electronic structure.

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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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Synthetic, spectral, structural and catalytic activity of infinite 3-D and 2-D copper(ii) coordination polymers for substrate size-dependent catalysis for CO2 conversion

Two copper(ii) coordination polymers, viz. [Cu2(OAc)4(mu4-hmt)0.5]n (1) and [Cu{C6H4(COO-)2}2]n¡¤2C9H14N3 (2), have been synthesized solvothermally and characterized. The solid-state structure reveals that 1 is an infinite three-dimensional (3D) motif with fused hexagonal rings consisting of Cu(ii) and hmt in a mu4-bridging mode, while 2 is an infinite two dimensional (2D) motif containing Pht-2 in a mu1-bridging mode. CP 1 has a two-fold interpenetrated diamondoid network composed of 4-connected sqc6 topology with the point symbol of {66}, while 2 has a Shubnikov tetragonal plane network possessing a 4-connected node with an sql topology with a point symbol of {44¡¤.62}-VS [4¡¤4¡¤4¡¤4¡¤?¡¤?]. Both CPs 1 and 2 serve as efficient catalysts for CO2-based chemical fixation. Moreover, 1 demonstrates one of the highest reported catalytic activity values (%yield) among Cu-based MOFs for the chemical fixation of CO2 with epoxides. 1 shows high efficiency for CO2 cycloaddition with small epoxides but its catalytic activity decreases sharply with the increase in the size of epoxide substrates. The catalytic results suggested that the copper(ii) motif-catalyzed CO2 cycloaddition of small substrates had been carried out within the framework, while large substrates could not enter into the framework for catalytic reactions. The high efficiency and size-dependent selectivity toward small epoxides on catalytic CO2 cycloaddition make 1 a promising heterogeneous catalyst for carbon fixation and it can be used as a recoverable stable heterogeneous catalyst without any loss of performance. The solvent-free synthesis of the cyclic carbonate from CO2 and an epoxide was monitored by in situ FT-IR spectroscopy and an exposed Lewis-acid metal site catalysis mechanism was proposed.

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