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Structural versatility and electronic structures of copper(i) thiocyanate (CuSCN)-ligand complexes

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

 

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Inorganic-organic hybrid high-dimensional polyoxotantalates and their structural transformations triggered by water

The first two inorganic-organic hybrid three-dimensional (3D) polyoxotantalates (POTas) and the first two inorganic-organic hybrid 2D POTas have been obtained. All of these high-dimensional POTas are built from a new-type POTa dimeric cluster {Cu(en)(Ta6O19)}2/{Cu(enMe)(Ta6O19)}2 (en = ethylenediamine, enMe = 1,2-diaminopropane) bridged by copper complexes. Interestingly, extended POTas 1 and 3 can undergo single-crystal to single-crystal structural transformations triggered by water.

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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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Copper(I)-mediated direct trifluoromethylthiolation of allylic halides with elemental sulfur and (trifluoromethyl)trimethylsilane

Abstract A new method has been developed for the copper-mediated trifluoromethylthiolation of allylic halides by using potassium fluoride, elemental sulfur, and (trifluoromethyl)trimethylsilane in anhydrous N,N-dimethylformamide. This protocol provides facile access to a variety of allylic trifluoromethyl thioethers in moderate to good yields under mild, ligand-free reaction conditions.

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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 1-acetyl-2-silyoxycycloheptane derivatives via highly stereoselective formal [5+2] cycloaddition reaction

A stereoselective [5+2] cycloaddition reaction using a new five-carbon unit, that has a dicobalt acetylene complex moiety and an enol silyl ether moiety, was developed. In the presence of a Lewis acid, the five-carbon unit reacted with an enol triisopropylsilyl ether to give a 1-acetyl-2- silyoxycycloheptane derivative, in which the three contiguous substituents on the seven-membered ring arrange cis to each other.

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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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Low temperature processed inverted planar perovskite solar cells by r-GO/CuSCN hole-transport bilayer with improved stability

Low temperature processed Perovskite solar cells (PSCs) are popular due to their potential for scalable production. In this work, we report reduced Graphene Oxide (r-GO)/copper (I) thiocyanate (CuSCN) as an efficient bilayer hole transport layer (HTL) for low temperature processed inverted planar PSCs. We have systematically optimized the thickness of CuSCN interlayer at the r-GO/MAPbI3 interface resulting in bilayer HTL structure to enhance the stability and photovoltaic performance of low temperature processed r-GO HTL based PSCs with a standard surface area of 1.02 cm2. With matched valence band energy level, the r-GO/CuSCN bilayer HTL based PSCs showed high power conversion efficiency of 14.28%, thanks to the improved open circuit voltage (VOC) compared to the only r-GO based PSC. Moreover, enhanced stability has been observed for the r-GO/CuSCN based PSCs which retained over 90% of its initial efficiency after 100 h light soaking measured under continuous AM 1.5 sun illumination.

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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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ANTIBACTERIAL COMPOSITIONS

Compounds of formula (I) have antibacterial activity: wherein: m is 0 or 1 ; Q is hydrogen or cyclopropyl; AIk is an optionally substituted, divalent C1-C6 alkylene, alkenylene or alkynylene radical which may contain an ether (-O-), thioether (-S-) or amino (-NR)- link, wherein R is hydrogen, -CN or C1-C3 alkyl; X is -C(=O)NR6-, -S(O)NR6-, -C(=O)O- or -S(=O)O- wherein R6 is hydrogen, optionally substituted C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, -Cyc, or -( C1-C3 alkyl)-Cyc wherein Cyc is optionally substituted monocyclic carbocyclic or heterocyclic having 3-7 ring atoms; Z is N or CH, or CF; R2 and R3 are as defined in the description.

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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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Revealing the Chemistry between Band Gap and Binding Energy for Lead-/Tin-Based Trihalide Perovskite Solar Cell Semiconductors

A relationship between reported experimental band gaps (solid) and DFT-calculated binding energies (gas) is established, for the first time, for each of the four ten-membered lead (or tin) trihalide perovskite solar cell semiconductor series examined in this study, including CH3NH3PbY3, CsPbY3, CH3NH3SnY3 and CsSnY3 (Y=I(3?x)Brx=1?3, I(3?x)Clx=1?3, Br(3?x)Cl x=1?3, and IBrCl). The relationship unequivocally provides a new dimension for the fundamental understanding of the optoelectronic features of solid-state solar cell thin films by using the 0 K gas-phase energetics of the corresponding molecular building blocks.

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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 polyknotted topological isomers of copper(I) 3,5-bis(4-pyridyl) pyrazolates

Two unprecedented 3D polyknotted isomers, arisen from different linkage modes of SCN-, were obtained from 3,5-bis(4-pyridyl)-1H-pyrazole (Hbppz) and CuSCN under different conditions.

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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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THERAPEUTIC COMPOUNDS AND COMPOSITIONS

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

 

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Synthesis, structure and fluorescence properties of a coordination polymer [Cu2(SCN)4(BPX)]n with 1D ladder-shaped structure

A coordination polymer, [Cu2(SCN)4(BPX)]n (BPX = 1,4-bis(pyridinium) xylol) was synthesized and characterized by IR spectrum, fluorescence spectrum and single crystal X-ray diffraction. Crystal structure revealed that the title compound crystallized in monoclinic system with space group P2(1)/c, a = 5.7540(7)A, b = 12.7203(15)A, c = 17.598(2)A, = 94.9940(10). Two SCN-ions served as bridging ligands to link two Cu(I) ions, giving rise to an eight-member ring. Furthermore, copper atom and sulfur atom of the eight-member ring bonded sulfur atom and copper atom of adjacent eight-member ring through the formation of Cu-S to form a small four-member ring. Thus, innumerable eight-member rings alternately linked four-member rings each other to form an infinite one-dimensional ladder-shaped structure.

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