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Stretchable and luminescent networks from copper(I)-coordinated main-chain thioether polymers

Emissive organometallic polymers integrated with the properties of conventional polymers have attracted increasing attention from researchers. Copper (I)-thioether (Cu(I)-thioether) complexes of small molecule has been extensively reported, which is in sharply contrast with much less investigated Cu(I)-thioether polymers. In this work, Cu(I)-thioether coordination structure has been successfully combined with polymer ligands to form emissive polymer networks. The resulted hybrid networks overcame many challenges in the Cu(I)-thioether small compounds. The as-prepared Cu(I)-thioether networks exhibited much improved thermal stability (degradation temperature: 220 C) compared with Cu(I)-thioether molecular clusters. Besides, the Cu(I)-thioether networks can be processed into uniform free-standing film with excellent stretchability (breaking strain up to 200%) which cannot be realized in the Cu(I)-thioether small molecular system. Finally, the luminescent property of copper-thiother was inherited in the polymer networks and emissive polymer films with good transparency, excellent thermal stability and high stretchability. Interestingly, the dynamic coordination between thioether and copper (I) enabled the self-healing ability of the polymer films. The damaged emissive and stretchable films were able to be autonomous self-healed under ambient conditions. This work sheds lights on the design and fabrication of Cu(I)-thioether materials for advanced applications.

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

 

A new application about 1111-67-7

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Heteroleptic Cu(I) complexes with aromatic diimines and phosphines: Synthesis, structure, photophysical properties and THz time domain spectroscopy

Nine novel copper(I) complexes with diphosphine and diimine ligands, namely [Cu(dpq)(xantphos)]BF4 (1), [Cu(dpq)(xantphos)]I (2), [Cu(dpq)(dppp)]BF4 (3), [Cu(dppz)(dppp)]BF4 (4), [Cu(dppz)(dppp)]I (5), [Cu(dppz)(pop)]I (6), [Cu(dpq)(pop)]I (7), [Cu(dpq)(pop)]Br (8), [Cu(dpq)(pop)]SCN (9) (dpq = pyrazino[2,3-f][1,10]phenanthroline, dppz = dipyrido[3,2-a:2?,3?-c]phenazine, xantphos = 9,9-dimethyl-4,5-bis(diphenylphosphanyl)xanthene, dppp = 1,3-bis(diphenylphosphino)propane, pop = 1,1?-[(Oxydi-2,1-phenylene)]bis[1,1-diphenylphosphine]), were characterized by single crystal X-ray diffraction, IR, elemental analysis, 1H NMR, 31P NMR, fluorescence spectra and terahertz time domain spectroscopy (THz-TDS). These nine complexes were synthesized by the reactions of copper salts, diimine ligands and various of P-donor ligands through one-pot method. Single crystal X-ray diffraction reveals that complex 9 is of a simple mono-nuclear structure while complexes 6 and 7 are of dimer structures. For complex 8, hydrogen bonds and C?H?pi interactions lead to the formation of a 1D infinite chain structure. Interestingly, complexes 1?5 show novel 2D or 3D network structures through C?H?pi interactions. In addition, complexes 1?3 and 6?9 exhibit interesting fluorescence in the solid state at room temperature. Among the nine complexes, complex 1 shows the highest quantum yield up to 37% and the lifetime of 1 is 6.0 mus. The terahertz (THz) time-domain spectra of these complexes were also studied.

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

 

Extended knowledge of Cuprous thiocyanate

Balanced chemical reaction does not necessarily reveal either the individual elementary reactions by which a reaction occurs or its rate law.HPLC of Formula: CCuNS. In my other articles, you can also check out more blogs about 1111-67-7

HPLC of Formula: CCuNS, Name is Cuprous thiocyanate, belongs to copper-catalyst compound, is a common compound. HPLC of Formula: CCuNSIn an article, authors is Kim, Minju, once mentioned the new application about HPLC of Formula: CCuNS.

Band-Tail Transport of CuSCN: Origin of Hole Extraction Enhancement in Organic Photovoltaics

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

 

More research is needed about Cuprous thiocyanate

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Application of 1111-67-7, Catalysts function by providing an alternate reaction mechanism that has a lower activation energy than would be found in the absence of the catalyst. In some cases, the catalyzed mechanism may include additional steps.In a article, 1111-67-7, molcular formula is CCuNS, introducing its new discovery.

Three cation-templated Cu(i) self-assemblies: synthesis, structures, and photocatalytic properties

Three novel inorganic-organic supramolecular compounds based on cuprous halide/pseudohalides, named [MAPB][CuBr3] (1), [MAPB]2[Cu4I8] (2) and [(PAPB)Cu2(SCN)4]n (3), where MAPB = 1,3-bis(4-aminopyridiniummethyl)-benzene and PAPB = 1,4-bis(4-aminopyridiniummethyl)-benzene, have been synthesized based on a self-assembly reaction under ambient conditions. The structures of compounds 1, 2 and 3 were explored using IR spectroscopy, elemental analyses, PXRD, thermal gravimetric analysis (TGA), UV-Vis diffuse reflectance spectra and single-crystal X-ray diffraction in the solid state. Compound 1 is a mononuclear complex, compound 2 is a tetranuclear cubane-like clusteric oligomer and compound 3 possesses a 2-D polypseudorotaxane structure. Besides, the optical band gap and photocatalytic degradation properties of compounds 1-3 were also investigated and the excellent photodegradation efficiency of 2 may be due to the existence of distinct weak hydrogen bonds and face-to-face pi-pi stacking interactions.

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

 

Discovery of Cuprous thiocyanate

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REGIO-SPECIFIC SYNTHESIS OF 4-BROMO-3-METHYL-5-PROPOXY-THIOPHENE-2-CARBOXYLIC ACID

This invention is directed to a five step regio-specific synthesis of 4-bromo-3-methyl-5-propoxy-thiophene-2-carboxylic acid compound of formula 16 comprising the steps of acetalating 3-methyl-thiophene-2-carbaldehyde in an alcohol solvent; iodinating the acetalated 3-methyl-thiophene-2-carbaldehyde in an non-protic polar or hydrocarbon solvent to yield the corresponding iodinated and acetalated 3-methyl-thiophene-2-carbaldehyde product; treating the iodinated and acetalated product with water to yield the corresponding 5-iodo-3-methyl-thiophene-2-carbaldehyde; oxidizing the 5-iodo-3-methyl-thiophene-2-carbaldehyde to the corresponding 5-iodo-3-methyl-thiophene-2-carboxylic acid in ketone solvent; Ullmann coupling of the 5-iodo-3-methyl-thiophene-2-carboxylic acid with alkali metal propoxide salt using a copper catalyst in propanol to yield 3-methyl-5-propoxy-thiophene-2-carboxylic acid; esterifying 3-methyl-5-propoxy-thiophene-2-carboxylic acid to yield the corresponding alkyl 3-methyl-5-propoxy-thiophene-2-carboxylate; brominating the 3-methyl-5-propoxy-thiophene-2-carboxylic acid to yield the corresponding alkyl 4-bromo-3-methyl-5-propoxy-thiophene-2-carboxylate; and basic hydrolyzing the alkyl 4-bromo-3-methyl-5-propoxy-thiophene-2-carboxylate with base to yield 4-bromo-3-methyl-5-propoxy-thiophene-2-carboxylic acid.

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

 

More research is needed about Cuprous thiocyanate

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Unusual Behaviour of the Thioether Function of the Ligand 1,8-Bis(3,5-dimethyl-1-pyrazolyl)-3,6-dithiaoctane (bddo) towards Transition-metal Salts. X-Ray Structures of a Green and a Red Modification of

Co-ordination compounds of the new ligand 1,8-bis(3,5-dimethyl-1-pyrazolyl)-3,6-dithiaoctane (bddo) with MCl2 (M = Fe, Mn, Ni, Co, Zn, Cu, or Cd), MBr2 (M = Mn, Co, Ni, or Zn), Cu(BF4)2, and CuX (X = BF4, NCS, Cl, Br, or I) are described.The general formula for the divalent metal is and for copper(I), .With CuCl2 two modifications were obtained.The green modification of crystallises in space group P21/n with a = 9,019(2), b = 28,671(5), c = 8,431(2) Angstroem, beta = 113,65(2) deg, R = 0,055, and R’= 0,066 for 1578 unique reflections 2?(I)>.The compound consists of Cu(bddo)Cl2 units.The copper atom is co-ordinated by two pyrazole nitrogens and two chloride atoms, in trans positions, in a distorted square-planar geometry.The red modification of crystallises in space group Pbcn with a = 9,397(4), b = 15,093(4), c = 15,142(4) Angstroem, Z = 4, R = 0,069, and R’= 0,089 for 864 unique reflections ?(I)>.This compound consists of CuCl2 units linked together by ligand molecules, thus forming chains with distinct C2 symmetry perpendicular to the chain axis.The copper atom is co-ordinated in a distorted-tetrahedral geometry by two pyrazole nitrogens and two chloride atoms in cis positions.The sulphur atoms do not participate in the co-ordination, although molecular-mechanics calculations show that the ligand bddo is not sterically hindered to form tetradentate mononuclear chelates, i.e. with a MN2S2 chromophore.The structures of the other divalent metal halides were established as being very similar to that of the red modification.For semi-co-ordination of one or both tetrafluoroborates is indicated by the i.r. spectrum.Solid state 13C n.m.r. spectra of the copper(I) compounds indicate that the S atoms show significant shifts, suggesting co-ordination.In the thiocyanate and iodide compounds both thioether sulphurs co-ordinate in an identical manner, whereas in the chloride and bromide compounds they co-ordinate in a different manner.

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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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METHOD FOR PRODUCING BIARYL COMPOUND

A method for producing a biaryl compound represented by the formula (2) Ar?Ar ??(2) wherein Ar represents an aromatic group which can have a substituent, comprising conducting a coupling reaction of a compound represented by the formula (1) Ar?Cl ??(1) wherein Ar represents the same meaning as defined above, in the presence of copper metal and a copper salt.

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

 

Awesome and Easy Science Experiments about Cuprous thiocyanate

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One-pot’ synthesis of two molybdenum/tungsten (VI)-copper(I) mixed metal clusters under catalysis of 1,10-phenathroline

Under the catalysis of 1,10-phenathroline (phen), (NH4) 2 M’S4 (M’ = Mo,W) reacts with CuSCN and dppm in mixed solvent MeCN/DMF (1:1) to yield two saddle-shaped clusters [WS 4Cu4(SCN)2 (dppm)3] ?3DMF?2CH3CN (1) and [MoS4Cu4(SCN) 2 (dppm)3]?4DMF (2) (dppm = bis (diphenylphosphino) methane). Compounds 1-2 were characterized by elemental analysis, IR, UV-Vis, 1H NMR, 31P NMR, and single-crystal X-ray diffraction. Each [M’S4]2- (M’ = Mo, W) anion coordinates to four Cu atoms through four bridging S atoms, and all S atoms are coordinated with two Cu atoms. In each cluster the four Cu atoms are almost in one plane, and the M’ atom is above the plane. Cluster 1 was characterized by luminescent with the lambdaem = 545 nm. The possible catalysis mechanism of phenathroline is discussed.

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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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Balancing electrical and optical losses for efficient 4-terminal Si-perovskite solar cells with solution processed percolation electrodes

The unprecedented rise in efficiency of perovskite-based photovoltaics has sparked interest in semi-transparent devices, particularly for tandem structures. Despite promising reports regarding efficiency and reduced parasitic absorption, many devices still rely on processes from the gas phase, compromising both applicability and cost factors. Here, we report all-solution perovskite solar cells with improved infrared transparency ideally suited as top-cells for efficient multi-junction device configurations. We demonstrate the functionality of copper(i) thiocyanate as antireflective layer and as selective contact between the transparent conductive oxide and the perovskite. This concept allows us to fabricate an opaque device with steady state efficiency as high as 20.1%. By employing silver nanowires with robust environmental stability as the bottom electrode, we demonstrate different regimes of device performance that can be described through a classical percolation model, leading to semi-transparent solar cells with efficiencies of up to 17.1%. In conjunction with the implementation of an infrared-tuned transparent conductive oxide contact deposited on UV-fused silica, we show a full device average transmittance surpassing 84% between 800 and 1100 nm (as opposed to 77% with PEDOT:PSS as the selective contact). Finally, we mechanically stacked optimized perovskite devices on top of high performing PERL and IBC silicon architectures. The measured imputed output efficiency of the 4-terminal perovskite-silicon solar cell was 26.7% and 25.2% for the PERL-perovskite and IBC-perovskite, respectively.

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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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Enantioselective Organocatalyzed Direct alpha-Thiocyanation of Cyclic beta-Ketoesters by N -Thiocyanatophthalimide

A new electrophilic thiocyanation reagent, N-thiocyanatophthalimide, was synthesized and applied to the first example of catalytic asymmetric electrophilic alpha-thiocyanation of various cyclic beta-ketoesters by the bifunctional cinchona alkaloid catalysis. Thus, a variety of chiral alpha-thiocyanato beta-ketoesters with a quaternary carbon center have been achieved in excellent yields (up to 99%) and high enantioselectivities (up to 94% ee) in a convenient manner.

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