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Discrete Supertetrahedral T5 Selenide Clusters and Their Se/S Solid Solutions: Ionic-Liquid-Assisted Precursor Route Syntheses and Photocatalytic Properties

Although supertetrahedral Tn sulfide clusters (n=2?6) have been extensively explored, the synthesis of Tn selenide clusters with n>4 has not been achieved thus far. Reported here are ionic-liquid (IL)-assisted precursor route syntheses, characterizations, and the photocatalytic properties of six new M-In-Q (M=Cu or Cd; Q=Se or Se/S) chalcogenide compounds, namely [Bmmim]12Cu5In30Q52Cl3(Im) (Q=Se (T5-1), Se48.5S3.5 (T5-2); Bmmim=1-butyl-2,3-dimethylimidazolium, Im=imidazole), [Bmmim]11Cd6In28Q52Cl3(MIm) (Q=Se (T5-3), Se28.5S23.5 (T5-4), Se16S36 (T5-5); MIm=1-methylimidazole), and [Bmmim]9Cd6In28Se8S44Cl(MIm)3 (T5-6). The cluster compounds T5-1 and T5-3 represent the largest molecular supertetrahedral Tn selenide clusters to date. Under visible-light illumination, the Cu-In-Q compounds showed photocatalytic activity towards the decomposition of crystal violet, whereas the Cd-In-Q compounds exhibited good photocatalytic H2 evolution activity. Interestingly, the experimental results show that the photocatalytic performances of the selenide/sulfide solid solutions were significantly better than those of their selenide analogues, for example, the degradation time of the organic dye with T5-2 was much shorter than that with T5-1, whereas the photocatalytic H2 evolution efficiencies with T5-3?T5-6 improved significantly with increasing sulfur content. This work highlights the significance of IL-assisted precursor route synthesis and the tuning of photocatalytic properties through the formation of solid solutions.

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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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Structural features of di(1-adamantyl)benzylphosphane complexes of Cu(I) and Ag(I)

The sterically bulky di(1-adamantyl)benzylphosphane (L) reacts with the copper(I) compounds, CuX (X = Cl, Br, I and SCN), in a 1:1 ratio to give the salts CuXL. Single crystal X-ray structures for X = Cl, Br and SCN, show that the complexes exist as dimeric species of the type [Cu2X2L2] with the X groups bridging to give each copper a distorted trigonal-planar coordination geometry with a ?PX2? donor site. When [Cu(CH3CN)4]BF4reacts with L in a 1:2 ratio, the two-coordinated complex [CuL2]BF4was formed which has a P?Cu?P angle of 169.46(6), reflecting the influence of the adamantyl groups. The silver(I) 1:2 compound, [AgClL2], has a ?ClP2? donor set with a distorted P?Ag?P bond angle of about 149.02(5). The reduced coordination numbers, irregular structures and distortions of selected angles are a result of the steric bulk (large cone angle) of L. Some of these structural features may also assist in understanding why Pd(0) complexes of L are effective catalysts for the Sonogashira coupling reactions of arylchlorides and alkynes.

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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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Complexes of copper(I) thiocyanate with monodentate phosphine and pyridine ligands and the P(,N)-donor diphenyl(2-pyridyl)phosphine

Copper(I) thiocyanate derivatives were prepared by the reaction of CuNCS with pyridine (py) and tertiary monophosphine ligands [PR3 in general; in detail: PPh3, triphenylphosphine, P(4-FPh)3, tris(4-fluorophenyl)phosphine)], as well as the potentially bidentate ligand diphenyl(2-pyridyl)phosphine (PPh2py). Mechanochemical methods were used in some cases to investigate stoichieometries that were not easily accessible by conventional solution syntheses. Three forms of the resulting adducts of CuNCS/PR3/py-base (1:3-n:n) stoichiometry-all containing four-coordinate copper(I) atoms and monodentate N-thiocyanate groups-were confirmed crystallographically. Mononuclear arrays are defined for [(PPh2py)3-n(py)nCuNCS], n = 0, 1, 2, the monodentate thiocyanate being N-coordinated in all; two polymorphs are observed for the n = 2 complex, both crystallizing in monoclinic P21 (Z = 2) cells with similar cell dimensions, but with aromatic components eclipsed about the Cu-P bond in the PPh3 complex, and staggered in the PPh2py complex. Bridging thiocyanate groups are found in the 1:1:1 CuNCS/PPh2py/2-methylpyridine (mpy) and P(4-FPh)3/mpy complexes, wherein centrosymmetric dimers with eight-membered central rings are obtained: [(R3P)(mpy)Cu(NCS)2Cu(PR3)(mpy)], as is also the case in the parent 1:2 CuNCS/PPh2py adduct [(pyPh2P)2Cu(NCS)2Cu(PPh2py)2]. For the 1:1:1 CuNCS/P(4-FPh)3/py and PPh3/Brmpy (Brmpy = 3-bromo-4-methylpyridine) adducts, and, likely, CuNCS/PPh2py/py (1:1:1), single-stranded polymers of the form [?Cu(NCS)(PR3)(py-base)(Cu)?](?|?) with linearly bridging NCS ligands were obtained. Some derivatives, representative of all forms, display medium to strong green to blue luminescence when excited with radiation at 365 nm. The 31P CPMAS NMR spectroscopic data clearly differentiate the inequivalent phosphorus positions within each system, showing a wide range of 1J(31P,63/65Cu) values ranging from 965 Hz for [Cu(NCS)(PPh2py)3] to 1540 Hz for dimeric [(4-FPh)3P(mpy)Cu(NCS)2Cu(P(4-FPh)3)(mpy)], reflecting the large variations in the Cu-P bond length.

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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 conductive radical cation salts based on methylenediselenotetraselenafulvalene (MDSe-TSF): A sign of superconductivity in kappa-(MDSe-TSF)2Br below 4 K

Seven conductive radical cation salts based on MDSe-TSF (methylenediselenotetraselenafulvalene) have been synthesized by electrocrystallization in the presence of Cl-, Br-, I3-, I2Br-, PF6-, ClO4-, and Cu(NCS)2- counter anions. The crystal appearances of these salts fairly depend on the anions employed. X-ray crystallographic analyses have revealed that the PF6 and ClO4 salts in the shape of brown thin plates adopt the theta-type structures characterized by the herringbone arrangement of donor stacks, whereas the Cl and Br salts in the shape of black thick plates favor the kappa-type structures with the orthogonal arrangement of donor dimers. Regardless of different crystal appearances or crystal packing patterns, all these salts show high conductivity (> 102 S cm-1) at room temperature and retain metallic properties down to 4.2 K. Of them, the Br salt shows a weak but distinct diamagnetic shielding signal below 4 K in the dc magnetization measurement under zero-field-cooled (ZFC) condition, suggesting a sign of superconductivity. The band calculations of both PF6 and Br salts demonstrate closed Fermi surfaces indicative of two-dimensional molecular conductors.

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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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Improved CuSCN-ZnO diode performance with spray deposited CuSCN

P-type copper(I) thiocyanate (beta-CuSCN) was deposited using a pneumatic micro-spray gun from a saturated solution in propyl sulphide. An as-produced 6 mum CuSCN film exhibited a hole mobility of 70 cm 2/V¡¤s and conductivity of 0.02 S¡¤m-1. A zinc oxide (ZnO) nanorod array was filled with CuSCN, demonstrating the capability of the process for filling nanostructured materials. This produced a diode with a n-type ZnO and p-type CuSCN junction. The best performing diodes exhibited rectifications of 3550 at ¡À 3 V. The electronic characteristics exhibited by the diode were attributed to a compact grain structure of the beta-CuSCN giving increased carrier mobility and an absence of cracks preventing electrical shorts between electrode contacts that are typically associated with beta-CuSCN films.

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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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Fabrication of CH3NH3PbI3 perovskite-based solar cells: Developing various new solvents for CuSCN hole transport material

Copper (I) thiocyanate (CuSCN) is a cost-competitive hole selective contact for the emerging organic-inorganic hybrid perovskite solar cells. However, limitation of solvent is the main issue for getting an optimal thickness for pin-hole free selective contacts. We have developed various solvents such as mixture of propylsulfide with chlorobenzene (1:1), isopropanol with methylammonium iodide (10 mg/ml) and propylsulfide + isopropanol (1:2) + MAI (10 mg/ml) for dissolving CuSCN. It was found that perovskite layer was more stable once CuSCN coating laid on the top surface using the propylsulfide + isopropanol (1:2) + MAI (10 mg/ml) solvent than conventional propylsulfide by doctor blade technique. By employing low temperature solution-process techniques, power conversion achieved over 10% under full sun illumination by the proposed mixed solvent. CuSCN continues to offer promise as a chemically stable and straightforward replacement for the commonly used expensive organic hole conductor (2,2?,7,7?-tetrakis-(N,N-di-p-methoxyphenylamine)9,9?-spirobifluorene (Spiro-OMeTAD)).

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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-OPTIONALLY HYDROGENATED ISOQUINOLINE COMPOUNDS, PHARMACEUTICAL COMPOSITIONS AND PHARMACEUTICAL METHOD OF USE

The invention concerns a heterocyclene derivative of the formula I wherein Ar1 is optionally substituted phenyl, naphthyl or a 9- or 10-membered bicyclic heterocyclic moiety; A1 is a direct link to X1 or (1-3C)alkylene; X1 is oxy, thio, sulphinyl, sulphonyl or imino; Ar2 is optionally substituted 5-membered heterocyclene moiety; R1 is (1-4C)alkyl, (3-4C)alkenyl or (3-4C)alkynyl; and R2 and R3 together form a group of the formula -A2-X2-A3- which, together with the carbon atom to which A2 and A3 are attached, defines a ring having 5 to 7 ring atoms, wherein each of A2 and A3 is (1-3C)alkylene and X2 is oxy, thio, sulphinyl or sulphonyl; or a pharmaceutically-acceptable salt thereof. The compounds of the invention are inhibitors of the enzyme 5-lipoxygenase

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

 

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Condensed pyridazinyl guanidines, their production and use

Pyridazinyl guanidines of the formula: wherein ring A is a benzene ring or a nitrogen-containing 6-membered aromatic ring, each of which may be substituted; and R1is an aromatic ring group which may be substituted, or a salt thereof, which have activity for inhibiting Na-H exchange and are useful as a prophylactic/therapeutic agent for ischemic cardiovascular diseases such as myocardial infarction and arrythmia.

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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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Three pillared-layered inorganic-organic hybrid polymers with efficient luminescence

Three pillared-layered inorganic-organic hybrid polymers, namely, [Cu2(4,4?-Hbpt)(SCN)2]n (1), [Cd(4,4?-Hbpt)(SCN)2]n (2), and [Cd(4,4?-Hbpt)(SCN)2¡¤CH3CN]n (3) were synthesized via layer diffusion methods. In all three complexes, there exist 2-D neutral wave-like d10 metal thiocyanate layers (for 1, [Cu2(SCN)2]n, and for 2 and 3, [Cd(SCN)2]n) with (4, 4) topology, which are further connected by bidentate 4,4?-Hbpt ligands to form 3-D structures with the primitive cubic topology. The results of photoluminescence and thermogravimetric analyses indicate that the three complexes are good candidates as luminescent materials. This paper provides a strategy to synthesize a novel family of pillared-layered inorganic-organic hybrid polymers constructed with layered d10 metal thiocyanate layers and conjugated organic spacers at the molecular engineering level, as well as the discovery of new patterns of crystallization at the crystal engineering level.

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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 different 1D-chains in the structures of the copper(I) coordination polymers based on bidentate Schiff-base building units and thiocyanate anions as bridging ligands

The reaction of the bidentate Schiff-base ligands (3,4,5-MeO-ba)2en (L1) and (4-Me-ba)2en (L2) with Cu(SCN) in CH3CN yielded two copper(I) coordination polymers [Cu(L1)(SCN)]n (1) and [Cu(L2)(SCN)]n (2), which have been characterized by elemental analyses, IR- and 1H NMR-spectroscopy, and X-ray crystallography. The non-centrosymmetric structures of both Cu(I) complexes consist of an one-dimensional polymeric chain in which copper(I) ions are bridged by two thiocyanate groups bonding in an end-to-end fashion. The Cu(I)?Cu(I) separation is 5.604 A in 1 and 5.706 A in 2.

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