Our Top Choice Compound: CCuNS

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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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Formamide C-H bond activation has been achieved under oxidative conditions, using a copper catalyst and tert-butyl hydroperoxide (TBHP) as the external oxidant (see scheme). This oxidative coupling of a range of dialkyl formamides provides an easy, phosgene-free route for the selective synthesis of Z-enol carbamates and 2-carbonyl-substituted phenol carbamates in high yields. 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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Copper(i) thiocyanate (CuSCN) is a promising semiconductor with an expansive range of applications already demonstrated. Belonging to the group of coordination polymers, its structure can be easily modified, for example via ligand (L) coordination. In this work, we have analyzed in detail the crystal structures of 26 CuSCN-L complexes that exhibit diverse structures changing from the 3D networks of the parent CuSCN to 2D sheet, 1D ladder, 1D zigzag chain, 1D helical chain, and a 0D monomer as well as intermediate bridged structures. We outline herein the basic structural design principles based on four factors: (1) Cu(i) geometry, (2) CuSCN?:?L ratio, (3) steric effects, and (4) supramolecular interactions. In addition, we employ density functional theory to study the electronic structures of these 26 complexes and find that the opto/electronic properties vary over a wide range, e.g., widened or reduced fundamental band gaps, restricted hole transport due to Cu-SCN network disruption, and the possibility of electron transport through the ligand states. We also observe a correlation between the electronic properties and the dimensionality of the Cu-SCN network. Lowering the dimensionality of the 3D structure to 2D, 1D, and 0D by increasing the number of coordinating ligands, the dispersion and the width of the top valence bands decrease whereas the energy difference between the Cu and SCN states expands. Aliphatic ligands in most cases do not generate electronic states in the band gaps whereas aromatic ligands give rise to states between the Cu and SCN states that lead to optical absorption and emission in the visible range. This study provides guidelines for developing coordination polymer semiconductors based on the Cu-SCN network. The 2D structure is identified as a promising platform for designing new CuSCN-based materials as it retains the carrier transport properties while allowing for properties tailoring through ligand coordination.

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

 

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Molecular surfactants are widely used to control low-dimensional morphologies, including 2D nanomaterials in colloidal chemical synthesis, but it is still highly challenging to accurately control single-layer growth for 2D materials. A scalable stacking-hinderable strategy to not only enable exclusive single-layer growth mode for transition metal dichalcogenides (TMDs) selectively sandwiched by surfactant molecules but also retain sandwiched single-layer TMDs’ photoredox activities is developed. The single-layer growth mechanism is well explained by theoretical calculation. Three types of single-layer TMDs, including MoS2, WS2, and ReS2, are successfully synthesized and demonstrated in solar H2 fuel production from hydrogen-stored liquid carrier?methanol. Such H2 fuel production from single-layer MoS2 nanosheets is COx-free and reliably workable under room temperature and normal pressure with the generation rate reaching ?617 mumole g?1 h?1 and excellent photoredox endurability. This strategy opens up the feasible avenue to develop methanol-storable solar H2 fuel with facile chemical rebonding actualized by 2D single-layer photocatalysts.

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

 

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Organic hole transport materials, such as N 2,N 2,N 2?,N 2?,N 7,N 7,N 7?,N 7?-octakis(4-methoxyphenyl)-9,9?-spirobi[9H-fluorene]-2,2?,7,7?-tetramine (Spiro-OMeTAD), are commonly used as the hole transport materials in efficient perovskite solar cells, but the chemical synthetic procedure may increase the cost of the photovoltaic devices. On the other hand, inorganic hole transport materials, such as copper(I) thiocyanate (CuSCN) or copper(I) iodide (CuI), have potential for the manufacture of efficient and low-cost perovskite solar cells, but the performance of these devices is still imperfect. In this study, we demonstrate the use of an inorganic CuSCN and organic N,N?-di(1-naphthyl)-N,N?-diphenyl-(1,1?-biphenyl)-4,4?-diamine (NPB) hybrid bilayer as an alternative hole transport layer for planar CH3NH3PbI3 perovskite solar cells. The electronic behavior of the bilayer and the performance of the corresponding devices were discussed. As a result, the power conversion efficiency (PCE) for the best cells at AM1.5G illumination with a shadow mask was 12.3%.

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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 copper-catalyzed C-Si bond formation between N-halogenated amides and Si-B reagents is described. This oxidative coupling enables the silylation of C(sp3)-H bonds alpha to an amide nitrogen atom. The utility of the new method is demonstrated for sulfonamides, and N-chlorination with tBuOCl and C-H silylation employing CuSCN/4,4?-dimethoxy-2,2?-bipyridine as catalyst can be performed without purification of the N-Cl intermediate.

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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 this paper we present lomefloxacin’s (HLm, 2nd generation fluoroquinolone antibiotic agent) organic and inorganic derivatives: aminomethyl(diphenyl)phosphine (PLm), its oxide as well as new copper(I) iodide or copper(I) thiocyanate complexes with PLm and 2,9-dimethyl-1,10-phenanthroline (dmp) or 2,2?-biquinoline (bq) as the auxiliary ligands. The synthesized compounds were fully characterised by NMR, UV?Vis and luminescence spectroscopies. Selected structures were analysed by theoretical DFT (density functional theory) methods. High stability of the complexes in aqueous solutions in the presence of atmosferic oxygen was proven. Cytotoxic activity of all compounds was tested towards three cancer cell lines (CT26 – mouse colon carcinoma, A549 – human lung adenocarcinoma, and MCF7 – human breast adenocarcinoma). All complexes are characterised by cytotoxic activity higher than the activity of the parent drug and its organic derivatives as well as cisplatin. Studied derivatives as well as parent drug do not intercalate to DNA, except Cu(I) complexes with bq ligand. All studied complexes caused single-stranded cleavage of the sugar?phosphate backbone of plasmid DNA. The addition of H2O2 caused distinct changes in the plasmid structure and led to single- and/or double-strain plasmid cleavage. Studied compounds interact with human serum albumin without affecting its secondary structure.

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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 this work, soluble two-dimensional (2D) material of antimonene quantum sheets (AMQSs) is used to form a bilayer hole extraction layer (HEL) with CuSCN. It proves that the application of AMQSs helps to passivate surface defects of CuSCN, resulting in diminished recombination loss and depressed exciton quenching effect, and thereby achieving improved photovoltaic performance. In OPVs based on poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b;4,5-b?]dithiophene-2,6-diyl-alt-(4-(2-ethylhexyl)-3-fluorothieno[3,4-b]thiophene-)-2-carboxylate-2-6-diyl)]: [6,6]-phenyl C71-butyric acid methyl ester (PTB7-Th:PC71BM), over 12% enhancement of power conversion efficiency (PCE) is observed compared to that of the reference cell fabricated with pure CuSCN as an HEL. The advantage of the bilayer CuSCN/AMQS HEL is also confirmed in non-fullerene systems of PBDB-T-2F:IT-4F and PTB7-Th:ITIC. In a cell based on PBDB-T-2F:IT-4F, a PCE of 10.14% was obtained after application of AMQSs, which improved by about 10% compared to that of the reference cell using pure CuSCN as an HEL. Furthermore, cells based on CuSCN and CuSCN/AMQS HEL exhibit superior air stability. The use of a bilayer CuSCN/AMQS HEL provides a promising approach to obtain efficient and stable organic 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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Compounds of general formula (I) and compositions comprising compounds of general formula (I) that modulate pyruvate kinase are described herein. Also described herein are methods of using the compounds that modulate pyruvate kinase in the treatment of diseases.

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