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Construction of [(eta5-C5Me5)MoS 3Cu3]-based supramolecular assemblies from the [(eta5-C5Me5)MoS3(CuNCS) 3]- cluster anion and multitopic ligands with different symmetries

The assembly of a new family of [(eta5-C5Me 5)MoS3Cu3]-supported supramolecular compounds from a preformed cluster [PPh4][(eta5-C 6Me5)MoS3(CuNCS)3]¡¤DMF (1¡¤DMF) with four multitopic ligands with different symmetries is described. Reactions of 1 with 1,2-bis(4-pyridyl)ethane (bpe) (Cs symmetry) or 1,4-pyrazine (1,4-pyz) (D2h symmetry) in aniline gave rise to two polymeric clusters {[{(eta5-C5Me 5)MoS3Cu3}2(NCS)3(mu- NCS)(bpe)3]¡¤3aniline}n (2) and [(eta5- C5Me5)MoS3Cu3(1,4-pyz)(mu-NCS) 2]n (3). On the other hand, solid-state reactions of 1 with 2,4,6-tri(4-pyridyl)-1,3,5-triazine (tpt) (D3h symmetry) or 5,10,15,20-tetra(4-pyridyl)-21H,23H-porphyrin (H2tpyp) (D 4h symmetry if 21H and 23H of the H2tpyp are omitted) at 100C for 12 h followed by extraction with aniline yielded another two polymeric clusters {[(eta5-C5Me5)MoS 3Cu3(tpt)(aniline)(NCS)2]¡¤0. 75aniline¡¤0.5H2O}n (4) and {[(eta5- C5Me5)MoS3Cu3(NCS)(mu-NCS)(H 2tpyp)0.4(Cu-tpyp)0.1] ¡¤2aniline¡¤2.5benzene}n (5). These compounds were characterized by elemental analysis, IR spectra, UV-vis spectra, 1H NMR, and X-ray analysis. Compound 2 consists of a 2D (6,3) network in which [(eta5-C5Me5)MoS3Cu3] cores serve both a T-shaped three-connecting node and an angular two-connecting node to interconnect other equivalent units through single bpe bridges, double bpe bridges, and mu-NCS bridges. Compound 3 has a 3D diamondlike framework in which each [(eta5-C5Me5)MoS 3Cu3] core, acting as a tetrahedral connecting node, links four other neighboring units by 1,4-pyz bridges and mu-NCS bridges. Compound 4 contains a honeycomb 2D (6,3)core(6,3)tpt network in which each cluster core, serving a trigonal-planar three-connecting node, links three pairs of equivalent cluster cores via three tpt lignads. Compound 5 has a rare scalelike 2D (4,62)core(42,6 2)ligand network in which each cluster core acts as a T-shaped three-connecting node to link with other equivalent ones through mu-NCS bridges and H2tpyp (or Cu-tpyp) ligands. The results showed that the formation of the four different multidimensional topological structures was evidently affected by the symmetry of the ligands used. In addition, the third-order nonlinear optical properties of 1-5 in aniline were also investigated by using Z-scan techniques at 532 nm.

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

 

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Compositionally tunable photoluminescence emission in Cu 2ZnSn(S1-xSex)4 nanocrystals

Inorganic nanostructures: Alloyed Cu2ZnSn(S1-xSe x)4 wurtzite nanocrystals (10nm in size) with a varying composition (x=0-1) were synthesized using a colloidal hot injection route. A photoluminescence (PL) emission study of these nanocrystals shows a compositionally tunable band-gap ranging between 0.9-1.4eV that directly correlates to the sulfur-to-selenium ratio (see picture). Copyright

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

 

Archives for Chemistry Experiments of Cuprous thiocyanate

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Monomere Alkin-stabilisierte Kupfer(I)-Halogenid- und Kupfer(I)-Pseudohalogenid-Verbindungen; Kristallstructur von <(eta5-C5H4SiMe3)2Ti(C<*>CPh)2>CuCl

The reaction of Me3SiC<*>CSiMe3 (1), LnMC<*>CSiMe3 (4a, LnM = Cp(CO)2Fe; 4b, LnM = Cp(CO)3Mo> and E(C<*>CR)2 (6, E = Me2Si; 8, E = (eta5-C5H4SiMe3)2Ti; R is a singly bonded organic ligand) with CuX (2) (X is a halide or pseudohalide) is described. 1 and 4 react with CuX (2a, X = Cl; 2b X = Br; 2c, X = I; 2d, X = OSO2CF3) to yield the dimeric compounds <(eta2-Me3SiC<*>CSiMe3)CuX>2 (3a, X = Cl; 3b, X = Br; 3c, X = I; 3d, X = OSO2CF3) or <(eta2-LnMC<*>CSiMe3)CuX>2 (5a, LnM = Cp(CO)2Fe, X = Cl; 5b, LnM = Cp(CO)3Mo, X = Cl) respectively.In these compounds the C2 building block is eta2-coordinated to a CuX moiety and by the formation of copper-X-bridges (Cu2X2) a dimer is formed.However, the reaction of Me2Si(C<*>CSiMe3)(C<*>CR) (6a, R = SiMe3; 6b, R = H) with CuX (2) (X = Cl, Br, OSO2CF3, O2CMe) affords polymeric CSiMe3)(eta2-C<*>CR)Cu2X2>>n (7a, R = SiMe3, X = Cl; 7b, R = SiMe3, X = Br; 7c, R = H, X = Cl; 7d, R = H, X = Br; 7e, R = SiMe3, X = OSO2CF3; 7f, R = SiMe3, X = O2CMe) in high yields.In 7a-7f each alkynyl fragment is eta2-coordinated to a CuX unit.While the reaction of 6a or 6b with CuX yields polymeric 7a-7f, the organometallic, 1,4-diyne RC<*>C--C<*>CR ( = (eta5-C5H4SiMe3)2Ti; 8a, R = Ph; 8b, R = SiMe3) affords with CuX (2a, X = Cl; 2b, X = Br; 2c, X = I; 2e, X = CN; 2f, X = SCN) the dinuclear compounds <(eta5-C5H4SiMe3)2Ti(C<*>CR)2>CuX (9a, R = Ph, X = Cl; 9b, R = SiMe3, X = Cl; 9c, R = SiMe3, X = Br; 9d, R = SiMe3, X = I; 9e, R = SiMe3, X = CN; 9f, R = SiMe3, X = SCN).Compounds 9a-9f feature a monomeric copper(I) halide or copper(I) pseudohalidemoiety, which is stabilized by the chelating effect of the alkynyl ligands on (C<*>CR)2. <(eta5-C5H4SiMe3)2Ti(C<*>CSiMe3)2>CuCl (9b) reacts with AgX (X = CN, SCN, O2CMe, O2CPh) to yield <(eta5-C5H4SiMe3)2Ti(C<*>CSiMe3)2>CuX (9e, X = CN; 9f, X = SCN; 9g, X = OC(O)Me; 9h, X = OC(O)Ph) by precipitation of AgCl.In addition, the bis(alkynyl)-ansa-titanocene <(eta5-C5H4)Me2Si(eta5-C5H3SiMe3)>Ti(C<*>CSiMe3)2 (10) yields with CuCl (2a) the dinuclear species <Ti(C<*>CSiMe3)2>CuCl (11).The identity of compounds 3, 5, 7, 9 and 11 is confirmed by analytical and spectroscopic (IR, MS, 1H, 13C NMR) data, and that of <(eta5-C5H4SiMe3)2Ti(C<*>CPh)2>CuCl (9a) is confirmed by X-ray analysis.Crystals of 9a are monoclinic, space group Pc with cell constant a = 992.6(7), b = 1210(1), c = 1335.5(7) pm, beta = 105.75(5) deg, V = 1543(2)x106 pm3 and Z = 2.Keywords: Alkynes, 1,4-Diynes; Copper(I) halides; Copper(I) pseudohalides

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

 

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PROCESS FOR THE PREPARATION OF METAL ACETYLACETONATES

The present invention provides an improved, economical and environmmentally benign process for metal complexes of acetylacetone having the general formula, M(acac)n wherein M is a metal cation selected from the group consisting of Fe, Co, Ni, Cu, Zn, Al, Ca, Mg, Mo, Ru, Re, U, Th, Ce, Na, K, Rb, Cs, V, Cr, and Mn etc., n is an integer which corresponds to the electrovalence of M, are obtained by reacting the corresponding metal hydroxide, metal hydrated oxide or metal oxide with a stoichiometric amount of acetylacetone and separating the product.

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

 

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Copper(I) thiocyanate coordination polymers with dimethylpyrazine: Synthesis, crystal structures, thermal and luminescence properties

The new copper(I) coordination polymers polyl(di-mu 2-thiocyanato-N,S)-(mu2-2,5-dimethylpyrazine-N,N)] dicopper(I) (I) and poly[di-mu2-thiocyanato-N,S)-(mu 2-2,3-dimethyl-pyrazine-N,N)] dicopper(I) (II) were prepared by the reaction of copper(I) thiocyanate with 2,3- and 2,5-dimethylpyrazine in acetonitrile. In all compounds different CuSCN sub-structures are found which are connected by the dimethylpyrazine ligands to multi-dimensional coordination networks. The thermal properties of all compounds were investigated using simultaneous differential thermoanalysis (DTA), thermogravimetry (TG) and mass spectrometry (MS) as well as temperature resolved X-ray powder diffraction, On heating, compound I and II loose all of the dimethylpyrazine ligands in an endothermic reaction and transform directly into copper(I) thiocyanate. Optical investigations show two excited states for both compounds in absorption and in luminescence measurements which are both, MC and LMCT in character.

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

 

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Monodisperse CuS nanodisks: Lowerature solvothermal synthesis and enhanced photocatalytic activity

Controllable synthesis of uniformly disk-shaped CuS nanostructures with a narrow size distribution was realized by a lowerature (150 C) solvothermal process using polyvinyl pyrrolidone (PVP) as the surfactant. Monodispersed nanodisks of pure CuS phase with an average diameter of ca. 500 nm could be obtained at a specific S/Cu molar ratio (xS/Cu) of raw materials, which was revealed to affect the phase structure and morphology of the product but the influence of PVP content (xPVP) is limited. The CuS nanodisks have a broad absorption in the visible region and superior photocatalytic performances for the degradation of RhB whose decomposition rate reaches 93% in 2 h, indicating a potential application in the field of wastewater treatment.

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

 

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Modifications of quinolones and fluoroquinolones: hybrid compounds and dual-action molecules

Abstract: This review is aimed to provide extensive survey of quinolones and fluoroquinolones for a variety of applications ranging from metal complexes and nanoparticle development to hybrid conjugates with therapeutic uses. The review covers the literature from the past 10?years with emphasis placed on new applications and mechanisms of pharmacological action of quinolone derivatives. The following are considered: metal complexes, nanoparticles and nanodrugs, polymers, proteins and peptides, NO donors and analogs, anionic compounds, siderophores, phosphonates, and prodrugs with enhanced lipophilicity, phototherapeutics, fluorescent compounds, triazoles, hybrid drugs, bis-quinolones, and other modifications. This review provides a comprehensive resource, summarizing a broad range of important quinolone applications with great utility as a resource concerning both chemical modifications and also novel hybrid bifunctional therapeutic agents. Graphical abstract: [Figure not available: see fulltext.].

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

 

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Oxazolidine derivatives having anti-diabetic and anti-obesity properties, their preparation and their therapeutic uses

Compounds of formula (I): STR1 wherein: R is an alkyl group; X is oxygen or sulfur; Y is hydrogen atom or –A–COOH, in which A is an alkylene group; Ar is aryl or substituted aryl group; and pharmaceutically acceptable salts and esters thereof, have use in the treatment or prophylaxis of diabetes, obesity, hyperlipemia, hyperglycemia, complications of diabetes, obesity-related hypertension and osteoporosis.

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

 

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Reaction of the framework 3d-organometallosiloxanes with acetylacetone

A reaction of acetylacetone with the framework sandwich-type metallosiloxanes (MOS) of general formula [PhSiO2]6M 6[PhSiO2]6, where M = Cu, Ni, Mn, was studied by GPC, 1H and 29Si NMR spectroscopy, X-ray diffraction, elemental and functional analysis. The reaction involved replacement of the metal atoms with the hydrogen atoms and is accompanied by the formation of the corresponding chelate complexes M(acac)2. Displacement of the metal from the framework MOS leads to the destruction of molecular skeleton and formation of phenylsiloxanes containing Si-OH groups. The yield and composition of the reaction products considerably depend on the nature of the metal in [PhSiO2]6M6[ThSiO2]6. A selective substitution of the metal leads to the stereoregular hexahydroxyhexaphenylcyclohexasiloxane, [PhSiO(PH)]6, cis-isomer. The structure and composition of the crystalline hexahydroxyhexaphenylcyclohexasiloxane obtained were confirmed by 29Si NMR spectroscopy, X-ray diffraction study, and functional analysis, while its TMS derivative was studied with 1H NMR spectroscopy and GPC. Using a framework manganese phenylsiloxane as an example, a reversible character of the process has been established and an alternative synthesis of this compound from hexahydroxyhexaphenylcyclohexasiloxane and Mn(acac)2 has been accomplished for the first time.

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

 

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Synthesis, characterization, spectroscopic and photophysical properties of new [Cu(NCS){(L-N)2 or (L?-N?N)}(PPh3)] complexes (L-N, L?-N?N = Aromatic nitrogen base)

The syntheses, spectroscopic characterization (IR, 1H and 31P NMR, ESI-MS) and conductivity studies of the mixed N,P-donor complexes of copper(I) thiocyanate: [Cu(NCS)(py)2-(PPh3)], (2), [Cu(NCS)(Mepy)(PPh3)]2, (3), [Cu(NCS)(phen)- (PPh3)], (4), [Cu(NCS)(bpy)(PPh3)], (5), [Cu(NCS)(bpy)-(PPh2py)], (6), [Cu(NCS)(py)(PPh2py)], (7), (py = pyridine; Mepy = 2-methylpyridine; phen = 1,10-phenanthroline, bpy = 2,2?-bipyridyl), together with single-crystal X-ray structural characterizations of 2, 3, 4 (new polymorph), 5 and 6 are reported, which provides an opportunity to study the effect of the introduction of a pair of nitrogen donors, both unidentate and chelate, on the bonding parameters of the Cu/NCS/P system. Cu-P and Cu-N2(ar) are found to be similar [2.1974(5) and 2.091(2), 2.070(1) A for py2 adduct 2, cf. 2.1748(9)-2.200(1) and 2.071(2)-2.106(4) A for the counterpart values for bidentate adducts 4-6]. However, Cu-N(CS) and Cu-N-C are 2.013(2) A and 157.4(2) for py2 adduct 2 and 1.946(2)-1.981(8) A and 166.7(2)-176.58(2) for bidentate counterparts 4-6. The change is attributed primarily to the closure in the N-Cu-N angle [99.58(8) for py2 2; 77.7(6)-80.5(3) for N?N-bidentate donors 4-6]. In consequence of the increased steric profile of the Mepy ligand, we find the stoichiometry diminished to 1:1:1, which resulted in the formation of [(Ph3P) MepyCu(NCSSCN)Cu(Mepy)(PPh3)] dimers. TDDFT/CPCM calculations were used to clarify the type of transitions involved in the UV/Vis absorption spectra, and the corresponding experimental photoemission data were acquired. The 31P CPMAS spectra of the copper derivatives exhibit distorted quartets that afford values for 1JCu,P. Furthermore, the quadrupole-induced distortion factors were calculated, and in the cases of 2, 4 and 5, the quadrupole coupling constants were obtained, on the basis of the X-ray structures. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.

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