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CuI Complexes (cui + complex)

Distribution by Scientific Domains

Chemistry	85%

Selected Abstracts

Synthesis and Characterisation of a New Cu(O2CNAllyl2)2 Carbamato Complex and an Unusual Polymeric CuI Complex [CuI4Cl4(NHAllyl2)4]n: New Insights into Metal Carbamato Chemistry

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 35 2009
Alberto Albinati
Abstract Transition-metal N,N -dialkylcarbamato complexes represent an interesting class of compounds that can be conveniently used as precursors for the controlled formation of inorganic compounds, typically oxides. They can also be used as convenient precursors for chemical grafting of metal oxides on oxide surfaces as well as for the synthesis of inorganic,organic hybrid materials. In this last case, the presence of double bonds on the complex would enable its covalent embedding into a polymer matrix through reaction with suitable monomers. To this aim, we addressed the synthesis of an allyl-functionalised copper carbamato complex. During the synthesis of the N,N -diallylcarbamato complex Cu(O2CNAllyl2)2 (Cu1), the formation of the crystalline and unusual polymeric CuI complex [CuI4Cl4(NHAllyl2)4]n (Cu2) was observed. The new compound was characterised by X-ray single crystal diffraction and FTIR, 1H and 13C NMR spectroscopic analysis. In an attempt to investigate the redox mechanism and the equilibria leading to the formation of the observed unusual CuI polymeric complex, gas chromatography coupled with mass spectrometry (GC,MS) experiments were carried out, which allowed us to identify 3,4-dimethylpyrrole as the oxidation product of the reaction, leading to the reduction of CuII to CuI.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source]

Silica-Immobilized NHC,CuI Complex: An Efficient and Reusable Catalyst for A3 -Coupling (Aldehyde,Alkyne,Amine) under Solventless Reaction Conditions

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 13 2008
Min Wang
Abstract A novel silica-immobilized NHC,CuI complex was developed and used as a highly efficient catalyst in the three-component coupling reactions of aldehydes, alkynes and amines (A3 -coupling). The reactions were applicable to aromatic and aliphatic aldehydes, alkynes and amines, and generated the corresponding propargylamines in good yields only in the presence of SiO2,NHC,CuI (2 mol-%) at room temp. under solvent-free reaction conditions. Moreover, the catalyst was quantitatively recovered from the reaction mixture by a simple filtration and reused for ten cycles with almost consistent activity.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source]

Novel Heteroleptic CuI Complexes with Tunable Emission Color for Efficient Phosphorescent Light-Emitting Diodes,

ADVANCED FUNCTIONAL MATERIALS, Issue 15 2007
Q. Zhang
Abstract A series of orange-red to red phosphorescent heteroleptic CuI complexes (the first ligand: 2,2,-biquinoline (bq), 4,4,-diphenyl-2,2,-biquinoline (dpbq) or 3,3,-methylen-4,4,-diphenyl-2,2,-biquinoline (mdpbq); the second ligand: triphenylphosphine or bis[2-(diphenylphosphino)phenyl]ether (DPEphos)) have been synthesized and fully characterized. With highly rigid bulky biquinoline-type ligands, complexes [Cu(mdpbq)(PPh3)2](BF4) and [Cu(mdpbq)(DPEphos)](BF4) emit efficiently in 20,wt,% PMMA films with photoluminescence quantum yield of 0.56 and 0.43 and emission maximum of 606,nm and 617,nm, respectively. By doping these complexes in poly(vinyl carbazole) (PVK) or N -(4-(carbazol-9-yl)phenyl)-3,6-bis(carbazol-9-yl) carbazole (TCCz), phosphorescent organic light-emitting diodes (OLEDs) were fabricated with various device structures. The complex [Cu(mdpbq)(DPEphos)](BF4) exhibits the best device performance. With the device structure of ITO/PEDOT/TCCz:[Cu(mdpbq)(DPEphos)](BF4) (15,wt,%)/TPBI/LiF/Al (III), a current efficiency up to 6.4,cd,A,1 with the Commission Internationale de L'Eclairage (CIE) coordinates of (0.61, 0.39) has been realized. To our best knowledge, this is the first report of efficient mononuclear CuI complexes with red emission. [source]

Electronic Properties of 3,3,-Dimethyl-5,5,-bis(1,2,4-triazine): Towards Design of Supramolecular Arrangements of N-Heterocyclic CuI Complexes

CHEMISTRY - A EUROPEAN JOURNAL, Issue 12 2007
Blandine Courcot Dr.
Abstract A new efficient and safe synthesis of 3,3,-dimethyl-5,5,-bis-(1,2,4-triazine) is presented. The electron-density distribution and electrostatic properties (charge, electrostatic potential) of this molecule were analyzed. These properties were derived from a high-resolution single-crystal X-ray diffraction experiment at 100,K and compared to the results obtained from ab initio DFT quantum-mechanical calculations. Comparisons of its electrostatic potential features and integrated atomic charges (quantum theory of atoms in molecules, QTAIM) have been made with those of related molecules such as bipyrimidine ligands. Two methods were used to derive integrated charges: one is based on the conventional analytical procedure and the second uses a steepest-ascent numerical algorithm. Excellent agreement was obtained between these two methods. Charges and electrostatic potential were used as predictive indices of metal chelation and discussed in the light of complexation abilities of the title compound and related molecules. The crystal structure of a CuI complex of 3,3,-dimethyl-5,5,-bis(1,2,4-triazine) is reported here. In the solid state, this complex forms a three-dimensional multibranch network with open channels in which counterions and solvent molecules are located. This architecture involves both cis and trans isomers of the title compound. [source]

Synthesis and Characterisation of a New Cu(O2CNAllyl2)2 Carbamato Complex and an Unusual Polymeric CuI Complex [CuI4Cl4(NHAllyl2)4]n: New Insights into Metal Carbamato Chemistry

Silica-Immobilized NHC,CuI Complex: An Efficient and Reusable Catalyst for A3 -Coupling (Aldehyde,Alkyne,Amine) under Solventless Reaction Conditions

Electronic Properties of 3,3,-Dimethyl-5,5,-bis(1,2,4-triazine): Towards Design of Supramolecular Arrangements of N-Heterocyclic CuI Complexes

Enantioselective Conjugate Addition of Dialkylzinc and Diphenylzinc to Enones Catalyzed by a Chiral Copper(I) Binaphthylthiophosphoramide or Binaphthylselenophosphoramide Ligand System

CHEMISTRY - A EUROPEAN JOURNAL, Issue 21 2004
Min Shi Prof. Dr.
Abstract The enantioselective conjugate addition of dialkylzinc or diphenylzinc to enones was catalyzed by a copper(I)-axially chiral binaphthylthiophosphoramide or binaphthylselenophosphoramide ligand system at room temperature (20,°C) or 0,°C, affording the Michael adducts in high yields with excellent ee for cyclic and acyclic enones. The enantioselectivity and reaction rate achieved here are one of the best results yet for the Cu-catalyzed conjugate addition to enones. It was revealed that this series of chiral phosphoramides was a novel type of S,N-bidentate ligands on the basis of 31P NMR and 13C NMR spectroscopic investigations. The mechanism of this asymmetric conjugate addition system has been investigated as well. We found that the acidic proton of phosphoramide in these chiral ligands play a significant role in the formation of the active species. A bimetallic catalytic process has been proposed on the basis of previous literature. The linear effect of product ee and ligand ee further revealed that the active species is a monomeric CuI complex bearing a single ligand [CuI:ligand 1:1]. [source]

Extended X-ray Absorption Fine Structure Study of Copper(I) and Copper(II) Complexes in Atom Transfer Radical Polymerization

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 11 2003
Tomislav Pintauer
Abstract Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy has been used to investigate structural features of CuIBr and CuIIBr2 complexes with dNbpy, PMDETA, Me6TREN, tNtpy, and Me4CYCLAM in various solvents {dNbpy = 4,4,-bis(5-nonyl)-2,2,-bipyridine, PMDETA = N,N,N,,N,,,N,, -pentamethyldiethylenetriamine, Me6TREN = tris[2-(dimethylamino)ethyl]amine, tNtpy = 4,4,,4,,-tris(5-nonyl)-2,2,:6,,2,,-terpyridine, Me4CYCLAM = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane}. The structures of the CuI and CuII complexes were found to depend on the solvent polarity and the number of nitrogen atoms in the ligand. Generally, in non-polar media and with monomers typically used in ATRP, CuI complexes preferred a tetracoordinate geometry, and were either ionic as observed in [CuI(dNbpy)2]+[CuIBr2], (CuI,NAV = 2.00 Å, CuI,BrAV = 2.25 Å) and [CuI(Me4CYCLAM)]+[CuIBr2], (CuI,NAV = 2.06 Å, CuI,BrAV = 2.23 Å), or neutral as in [CuI(PMDETA)Br] (CuI,NAV = 2.12 Å, CuI,BrAV = 2.33 Å), and [CuI(tNtpy)Br] (CuI,NAV = 2.03 Å, CuI,BrAV = 2.29 Å). The EXAFS analysis of CuIIBr2 complexes indicated a preference for a coordination number of five, such as in [CuII(dNbpy)2Br]+[Br], (CuII,NAV = 2.03 Å, CuII,BrAV = 2.43 Å), [CuII(PMDETA)Br2] (CuII,NAV = 2.03 Å, CuII,Br1,AV = 2.44 Å, CuII,Br2,AV = 2.64 Å) and [CuII(Me6TREN)Br]+[Br], (CuII,NAV = 2.09 Å, CuII -BrAV = 2.39 Å), with the exception of the neutral tetracoordinate [CuII(dNbpy)Br2] (CuII,NAV = 2.02 Å, CuII,BrAV = 2.36 Å), which has been observed in non-polar media. Additionally, polar media were found to favor bromide dissociation in [CuII(Me6TREN)Br]+[Br], and [CuII(PMDETA)Br2], as indicated by a decrease in the Br and Cu coordination numbers at the Cu- and Br- K -edges, respectively. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source]

Syntheses and Crystal Structures of Copper and Silver Complexes with New Imine Ligands , Air-Stable, Photoluminescent CuIN4 Chromophores

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 5 2003
Goutam Kumar Patra
Abstract A series of new imine ligands [1 (C12H12N2S2), 2 (C12H12N2S2), 3 (C24H18N4S2), and 5 (C30H27N7)] have been synthesized (1 and 2 are structural isomers). CuI and AgI complexes of the nonconjugated dithiophene-diimine ligands 1, 2 and the tripodal imine-amine ligand 5 have also been prepared and thoroughly characterized by spectroscopic techniques as well as by X-ray diffraction. In cyclic voltammetry at a glassy carbon milli electrode in anhydrous dichloromethane under dry N2, the corresponding CuI complexes [6 (2C12H12N2S2·CuClO4), 7 (2C12H12N2S2·CuClO4), and 12 (C30H27N7·CuClO4)] show quasi-reversible CuII/I couples with high redox potentials (1.001 V for 6, 0.958 V for 7, and 0.692 V for 12, vs. Ag/AgCl). This indicates that the ,-acid ligands 1, 2, and 5 preferentially stabilize copper(I) over copper(II). The CuIN4 chromophores in the complexes 6, 7, and 12 display photoluminescence in dichloromethane at room temperature. The related silver complexes of the same three ligands 10 (2C12H12N2S2·AgClO4), 11 (2C12H12N2S2·AgClO4), and 13 [C30H27N7·Ag(CH3CN)ClO4] reveal similar structural features but lack specific photophysical properties. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source]

Novel Heteroleptic CuI Complexes with Tunable Emission Color for Efficient Phosphorescent Light-Emitting Diodes,

Coordination-Driven Hierarchical Organization of ,-Conjugated Systems: From Molecular to Supramolecular ,-Stacked Assemblies

CHEMISTRY - A EUROPEAN JOURNAL, Issue 24 2010
Yishan Yao Dr.
Abstract The reaction of U-shaped, bimetallic, CuI complexes, assembled from a heteroditopic pincer, with cyano-capped ,-conjugated linkers gives a straightforward access to ,-stacked metallocyclophanes in good yields. In these assemblies, the ,-walls have an almost face-to-face arrangement. The versatility of this rational supramolecular synthesis is demonstrated with the use of linkers that have nanoscale lengths (up to 27.7,Å), different chemical compositions (oligo(para -phenylenevinylene)s OPVs, oligo(phenylene)s, oligo(phenylethynylene)s), and alternative geometries (linear, angular). Linkers that incorporate an internal pyridyne moiety can also be employed. X-ray diffraction studies revealed that the metallocyclophanes based on linear linkers self-organize into infinite ,-stacked columns in the solid state with intermolecular distances of about 3.6,Å. This approach, based on coordination-driven self-assembly, provides a novel and rational strategy for the stacking of extended ,-systems in the solid state. [source]

Electronic Excited-State Engineering

CHEMPHYSCHEM, Issue 3 2008
Nicola Armaroli Dr.
Long-living complexes: A CuI - bisphenanthroline complex exhibits a 15-fold prolongation of its excited state lifetime due to the planned intervention of an appended anthracene fragment (see picture). This elegant example of electronic excited-state engineering extends the range of possibilities for improving the photophysical properties of CuI complexes. [source]

CuI versus RuII: Dye-Sensitized Solar Cells and Beyond

CHEMSUSCHEM CHEMISTRY AND SUSTAINABILITY, ENERGY & MATERIALS, Issue 12 2008
Neil Robertson Dr.
Copper for the scientist cunning at his trade: RuII complexes have long played the central role in the photochemical conversion of sunlight and dye-sensitized solar cells (DSSCs). Recently, however, the first examples of DSSCs sensitized by CuI polypyridyl complexes were reported. CuI complexes have comparable photophysical and electrochemical properties to RuII complexes and offer similar function with a cheaper and more abundant metal. [source]