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Di(2-pyridyl) ketone complexes of CuI- and Cu II-containing iodide and thiocyanate ligands: An unusual case of a mixed-aldol condensation

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”

 

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Two type skeleton heterobimetallic trinuclear Cu-Mo-S clusters containing closo carborane diphosphine ligand 1,2-bis(diphenylphosphino)-1,2-dicarba-closo-dodecaborane

The carborane skeleton was introduced into the heterometallic sulfide cluster cores. Two heterobimetallic trinuclear Cu-Mo-S clusters with linear or butterfly-shaped skeleton containing 1,2-bis(diphenylphosphino)-1,2-dicarba-closo-dodecaborane have been synthesized by the reactions of (NH4)2MoS4 or (NH4)2MoOS3, CuSCN with 1,2-(PPh2)2-1,2-C2B10H10 (L) in dichloromethane and characterized by elemental analysis, FT-IR, UV/Visible, 1H and 13C NMR spectroscopy and X-ray structure determination.

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

 

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Carbon Nano-Onions as a Functional Dopant to Modify Hole Transporting Layers for Improving Stability and Performance of Planar Perovskite Solar Cells

Poly (3,4-ethylenedioxythiophene) polystyrene sulphonate (PEDOT:PSS) is the most widely used hole transporting layer (HTL) in planar perovskite solar cells, which shows excellent optical, electrical properties and good compatibility with low temperature, solution and flexible processing. Nevertheless, the acidic and hygroscopic property of PEDOT:PSS restricts its film conductivity and leads to the degradation of device stability. Herein, for the first time, we introduce the unprecedentedly zero-dimensional dopant of carbon nano-onions (CNOs) and the functionalized oxidized carbon nano-onions (ox-CNOs) to modify the PEDOT:PSS HTL. Besides the merits of high conductivity and suitable energy level, the CNOs and ox-CNOs modified PEDOT:PSS HTLs could provide a superior perovskite crystalline film with large-scale grains and orderly grain boundaries exhibiting a high surface tension with the hydrophobic property, resulting in a significant enhancement of PCE from 11.07% to 15.26%. Moreover, by suppressing the corrosion effect of PEDOT:PSS on ITO electrode, a dramatic improvement in the device stability has also been obtained.

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

 

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2-Pyridinecarboxylic acids

5-Etherified 2-pyridinecarboxylic acids, e.g. those of the formula STR1 or functional derivatives thereof, are hypotensive agents.

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

 

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Process for preparing 3,5-difluoroaniline

The invention provides a novel process for producing a 3,5-difluoroaniline compound by reacting a 2-halo-4,6-difluoroaniline with a diazotizing agent in the presence of a reducing agent to form a diazonium salt. Build-up of potentially dangerous diazonium salt is avoided by reducing the diazonium salt with the reducing agent, to form a 1-halo-3,5-difluorobenzene, contemporaneously with the diazotization reaction. The 1-halo-3,5-difluorobenzene is then aminated.

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

 

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Synthesis, spectral and crystal structures of two new copper(I) complexes of di-2-pyridyl ketone (DPK) containing uncoordinated N-protonated ligand; [(DPK)H][CuX2] (X = I and NCS)

Two new copper(I) complexes of di-2-pyridyl ketone (DPK); [(DPK)H][CuI2] (1) and [(DPK)H][(Cu{NCS)2] (2) have been prepared and characterized by spectroscopic and crystallographic methods. Both complexes are colored and exhibit very broad and strong MLCT bands in the visible region. The IR spectra of these complexes are measured and discussed. The structure determination of complex 1 shows that it consists of discrete [(DPK)H]+ cation contains N-H···N hydrogen bonds, and polymeric [CuI2]- anion. In the anion, each copper atom is in a distorted tetrahedral environment with Cu-I bond lengths from 2.570(4) to 3.072(4) A?. The structure of complex 2, which is similar to 1, features uncoordinated N-protonated di-2-pyridyl ketone cations and corrugated layers of [Cu(NCS)2](n), in which the copper atom is in a distorted tetrahedral CuS2N2 chromophore; Cu-N bond lengths are 1.954(2) and 1.958(2) A?, and Cu-S distances are 2.4120(8) and 2.4501(7) A?. (C) 2000 Elsevier Science Ltd.

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

 

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Synthesis of 1D {Cu6(mu3-SC3H 6N2)4(mu-SC3H6N 2)2(mu-I)2I4}n and 3D {Cu2(mu-SC3H6N2) 2(mu-SCN)2}n polymers with 1,3-imidazolidine-2-thione: Bond isomerism in polymers

The reaction of copper(I) iodide with 1, 3-imidazolidine-2-thione (SC 3H6N2) in a 1:2 molar ratio (M/L) has formed unusual 1D polymers, {Cu6(mu3-SC3H 6N2)4(mu-SC3H6N 2)2(mu-I)2I4}n (1) and {Cu6(mu3-SC3H6N2) 2(mu-SC3H6N2)4(mu-I) 4I2}n (1a). A similar reaction with copper(I) bromide has formed a polymer {Cu6(mu3-SC 3H6N2)2(mu-SC3H 6N2)4(mu-Br)4Br2} n (3a), similar to 1a, along with a dimer, {Cu2(mu- SC3H6N2)2(eta1-SC 3H6N2)2Br2} (3). Copper(I) chloride behaved differently, and only an unsymmetrical dimer, {Cu2(mu-SC3H6N2) (eta1-SC3H6N2)3Cl 2} (4), was formed. Finally, reactions of copper-(I) thiocyanate in 1:1 or 1:2 molar ratios yielded a 3D polymer, {Cu2(mu-SC 3H6N2)2(mu-SCN)2} n (2). Crystal data: 1, C9H18Cu 3I3N6S3, triclinic, P1, a = 9.6646(11) A, b = 10.5520(13) A, c = 12.6177(15) A, alpha = 107.239(2), beta = 99.844(2), gamma = 113.682(2), V = 1061.8(2) A3, Z = 2, R = 0.0333; 2, C4H 6CuN3S2, monoclinic, P21/c, a = 7.864(3) A, b = 14.328(6) A, c = 6.737(2) A, beta = 100.07(3), V = 747.4(5), Z = 4, R = 0.0363; 3, C12H 24Br2Cu2N8S4, monoclinic, C2/c, a = 19.420(7) A, b = 7.686(3) A, c = 16.706(6) A, beta = 115.844(6), V = 2244.1(14) A3, Z = 4, R = 0.0228; 4, C12H24Cl2Cu2N8S 4, monoclinic, P21/c, a = 7,4500(6) A, b = 18.4965(15) A, c = 16.2131(14) A, beta = 95.036(2), V = 2225.5(3) A3, Z = 4, R = 0.0392. The 3D polymer 2 exhibits 20-membered metallacyclic rings in its structure, while synthesis of linear polymers; 1 and 1a, represents an unusual example of I (1a)-S (1) bond isomerism.

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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’ll also look at important developments in the pharmaceutical industry because understanding organic chemistry is important in understanding health, medicine, the role of 1111-67-7, and how the biochemistry of the body works.Application In Synthesis of Cuprous thiocyanate

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Synthesis and properties of a Cu4(SCN)4 cubane cluster-based coordination polymer with a diamond net

A triply-interpenetrating diamondoid coordination polymer [Cu 4(SCN)4(tpom)]·2H2O (1, tpom = tetrakis(4-pyridyloxymethylene)methane) was prepared, which is built from an unprecedented pseudohalide cubane cluster Cu4(SCN)4 and tetrahedral tpom ligand. 1 exhibits high thermal stability and temperature-dependent photoluminescence behaviors resembling those of Cu 4Cl4 complexes.

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

 

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Study of the Hole Transport Processes in Solution-Processed Layers of the Wide Bandgap Semiconductor Copper(I) Thiocyanate (CuSCN)

Wide bandgap hole-transporting semiconductor copper(I) thiocyanate (CuSCN) has recently shown promise both as a transparent p-type channel material for thin-film transistors and as a hole-transporting layer in organic light-emitting diodes and organic photovoltaics. Herein, the hole-transport properties of solution-processed CuSCN layers are investigated. Metal-insulator-semiconductor capacitors are employed to determine key material parameters including: dielectric constant [5.1 (±1.0)], flat-band voltage [-0.7 (±0.1) V], and unintentional hole doping concentration [7.2 (±1.4) × 1017 cm-3]. The density of localized hole states in the mobility gap is analyzed using electrical field-effect measurements; the distribution can be approximated invoking an exponential function with a characteristic energy of 42.4 (±0.1) meV. Further investigation using temperature-dependent mobility measurements in the range 78-318 K reveals the existence of three transport regimes. The first two regimes observed at high (303-228 K) and intermediate (228-123 K) temperatures are described with multiple trapping and release and variable range hopping processes, respectively. The third regime observed at low temperatures (123-78 K) exhibits weak temperature dependence and is attributed to a field-assisted hopping process. The transitions between the mechanisms are discussed based on the temperature dependence of the transport energy. The wide bandgap p-type semiconductor copper(I) thiocyanate (CuSCN) has the potential to replace conventional hole-transport materials in numerous opto/electronics applications. This work provides a comprehensive analysis of the charge transport properties of solution-processed CuSCN layers. Various techniques are employed to evaluate the dielectric constant, flat-band voltage, unintentional doping concentration, density of states in the mobility gap, and hole-transport mechanisms.

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

 

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5-Substituted picolinic acid derivatives and an anti-hypertensive composition containing the same

5-Substituted picolinic acid derivatives represented by the formula (I): STR1 wherein R1 represents a straight or branched chain halogen-substituted alkyl group having 2 to 6 carbon atoms or a substituted phenyl group having the formula STR2 wherein R3 and R4, which may be the same or different, each represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a nitro group, an amino group, an N-alkyl-substituted amino group, an acylamino group, an acetyl group, an acyloxy group, a hydroxy group or a halogen-substituted alkyl group or R3 and R4, when taken together, represent a polymethylene chain; and R2 represents an –OM group wherein M represents a hydrogen, sodium, potassium, calcium, aluminium or magnesium atom, a straight or branched chain or cyclic alkoxy group having 1 to 6 carbon atoms, an aminoalkoxy group, a phenoxy group, a substituted phenoxy group, a 5-indanyloxy group, an acyloxyalkyloxy group having the formula STR3 wherein R5 represents a hydrogen atom or a methyl group and R6 represents a lower alkyl group having 1 to 6 carbon atoms, a phenyl group or a substituted phenyl group, or an amino group represented by the formula STR4 wherein R7 and R8, which may be the same or different, each represents a hydrogen atom, a lower alkyl group, or a phenyl group which are useful as anti-hypertensive agents, a process for preparing the above 5-substituted picolinic acid derivatives, and anti-hypertensive compositions containing the same.

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