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Heteroleptic neutral mononuclear cuprous complexes with dipyrrin derivatives and phosphine mixed-ligands including 1,3,7,9-tetramethyldipyrrin (1), 5-phenyl-1,3,7,9-tetramethyldipyrrin (2), 2,8-dibromo-1,3,7,9- tetramethyldipyrrin (3), 1,9-dichloro-5-phenyldipyrrin (4), 1,9-dibromo-5- phenyldipyrrin (5), 5-pentafluorophenyl-1,3,7,9-tetramethyldipyrrin (6) and 1,5,9-triphenyldipyrrin (7) have been synthesized and fully characterized. The central Cu(i) atoms of these complexes in general formulas of Cu(1-6)(PPh 3)2 (1a-6a) and Cu(1-6)(DPEphos) (1b-6b) [DPEphos = bis(2-diphenylphosphinophenyl)ether] all exhibit a pseudo-tetrahedral geometry, while complex Cu(7)(PPh3) (7a) is tricoordinated in a pyramidal conformation due to the large steric hindrance of ligand 7. The oxidation potentials assigned to oxidations of Cu(i)-Cu(ii) are extraordinarily low in the range of 0.36-1.02 V vs. Ag/AgCl compared with traditional [Cu(phen)(PP)] + analogues. Their emission maxima range from 495 to 595 nm in dichloromethane at room temperature with quantum yields of 0.05-4.03% and lifetimes on the order of nanoseconds. Unlike the characteristic MLCT emission in cationic Cu(i) complexes, the emissions are assigned to the dipyrrin-centered intraligand charge transition (ILCT) based on the fact that the increased conjugation within the dipyrrinato anion leads to a weaker metal-ligand interaction, thus preventing the mixing of pi orbitals of ligand and 3d orbitals of Cu(i) atom. This conclusion is also supported by electrochemical data and theoretical calculations.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Homogeneous palladium-catalyzed (Pd-catalyzed) cyclocarbonylation of unsaturated allylic alcohols and alkynols in the presence of hydrogen forms lactone products with important applications in the food, perfume, and polymer industry. In this work, the cyclocarbonylation of 2-methyl-3-buten-2-ol was studied for the first time using a very active Pd-DPEphos (bis[(2-diphenylphosphino)phenyl]ether) catalyst in the presence of the ionic liquid (IL) [BMIM]Cl (1-butyl-3-methylimidazolium chloride) in dichloromethane to selectively produce 4,4-dimethyl–butyrolactone. The effect of different parameters such as temperature, gas partial pressures, time of reaction, substrate and ligand concentrations were investigated and found to provide optimal conditions for lactonization (95 C, 28 bar (CO/H2/N2: 20/5/3)), 18 h, 0.1 M substrate, and 16 mol% DPEphos), which were significantly milder than previously reported systems for cyclocarbonylation. Importantly, the study further showed that presence of the IL in the reaction mixture provided stabilization of the catalyst system and prevented formation of Pd-black, which allowed reuse of the catalytic system in consecutive reactions after intermediate extraction of the lactone product.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Two neutral copper(I) complexes (1 and 2) bearing deprotonated 2-(4-nitro phenyl) imidazole[4,5-f]-1,10- phenanthroline (NPIP) and different phosphine ligands (bis[2-(diphenylphosphino) phenyl]ether (DPEphos) and PPh3) were synthesized and characterized. The molecular structure of a representative complex (1) was established by single-crystal X-ray diffraction. The complex features the metal in a distorted tetrahedral environment surrounded by two N atoms of the chelating NPIP ligand and two P atoms from DPEphos ligand. The emission spectra show that the two complexes exhibit yellow emission both in anhydrous ether and in the solid powder form. Density functional theory (DFT) calculation was carried out at the B3LYP/6-31G level to determine the electronic transition within the molecule.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 166330-10-5, Name is (Oxybis(2,1-phenylene))bis(diphenylphosphine), molecular formula is C36H28OP2. In a Article,once mentioned of 166330-10-5, Safety of (Oxybis(2,1-phenylene))bis(diphenylphosphine)

Two new mononuclear Cu(I) complexes based on 2-(2?-pyridyl) benzimidazolyl derivative ligand containing hole-transporting carbazole (L), [Cu(L)(DPEphos)](BF4) and [Cu(L)(PPh3)2] (BF4), where L = (4-(9H-carbazol-9-yl)phenyl)methyl-2-(2?- pyridyl)benzimidazole; DPEphos = bis[2-(diphenylphosphino)phenyl]ether and PPh3 = triphenylphosphine, have been synthesized and characterized on the basis of elemental analysis, 1H NMR and FT-IR spectra. The structures of the ligand L and the Cu(I) complexes were characterized by single crystal X-ray diffraction. The results reveal that in the Cu(I) complexes the central Cu(I) ions assume the irregular distorted tetrahedral geometry and are tetra-coordinated by the two nitrogen atoms from L ligand and two phosphorus atoms from ancillary ligands. The photophysical properties of the complexes were examined by using UV-vis, photoluminescence spectroscopic analysis. The complexes exhibit weak MLCT absorption bands ranging from 360 to 480 nm, and display strong orange phosphorescence in the solid states at room temperature, which is completely quenched in solutions.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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This work provides the synthesis, structural characterization, electrochemical and photophysical features, as well as the application in light-emitting electrochemical cells (LECs) of a novel heteroleptic copper(i) complex-[Cu(impy)(POP)][PF6], where impy is 3-(2-methoxyphenyl)-1-(pyridine-2-yl)imidazo[1,5-a]pyridine and POP is bis{2-(diphenylphosphanyl)phenyl}ether. This compound shows blue photoluminescence (PL, lambda = 450 nm) in solution and solid-state and excellent redox stability. Despite these excellent features, the electroluminescence (EL) response is located at ?550 nm. Although the EL spectrum of LECs is typically red-shifted compared to the PL of the electroluminescent material, a shift of ca. 100 nm represents the largest one reported in LECs. To date, the large shift phenomena have been attributed to (i) a change in the nature of the lowest emitting state due to a concentration effect of the films, (ii) a reversible substitution of the ligands due to the weak coordination to the Cu(i), and (iii) a change in the distribution of the excited states due to polarization effects. After having discarded these along with others like the irreversible degradation of the emitter during device fabrication and/or under operation conditions, driving conditions, active layer composition, and changes in the excited states under different external electrical stimuli, we attribute the origin of this unexpected shift to a lack of a thermally activated delayed fluorescence (TADF) process due to the solely ligand-centered character of the excited states. As such, the lack of a charge transfer character in the excited states leads to a blue-fluorescence and yellow-phosphorescence photo- and electro-responses, respectively. This corroborates recent studies focused on the design of TADF for heteroleptic copper(i) complexes. Overall, this work is a clear insight into the design of new copper(i) complexes towards the preparation of blue LECs, which are still unexplored.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Herein, we report the palladium-catalyzed synthesis of 3-arylpropionate esters starting from secondary benzylic ethers. With this investigation it could be shown that ethers are suitable starting materials in addition to the established carbonylation reactions of olefins, alcohols, or aryl halides.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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A Co(II)/Ag(I) synergistically catalyzed three-component reaction of isocyanide with terminal alkyne and water to afford alkynamide derivatives is reported. The insertion of monoisocyanide into the C-H bond of terminal alkynes is an efficient, straightforward, atom-economical route to alkynamides, which are useful synthons in organic synthesis. This synergistic process achieves the cleavage of a C-H bond and the construction of new C-C and Ca?O bonds under mild conditions through the reaction of Co(II)-activated isocyanides and a Ag(I)-complex-activated terminal alkyne. This reaction has broad substrate versatility and functional group tolerance.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Complexes of Pd(tcne) (tcne = tetracyanoethylene) containing bidentate ligands with large bite angles, bis<2-(diphenylphosphino)phenyl> ether (L1), 4,6-bis(diphenylphosphino)-10,10-dimethyl-10H-dibenzo<1,4>oxasiline (L2), 4,5-bis(diphenylphosphino)-2,8-dimethylphenoxathiine (L3), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (L4) and trans-5,6-bis(2-pyridyl)bicyclo<2.2.1>hept-2-ene (L6), were prepared and characterised.The compound 4,6-bis(diphenylphosphino)dibenzofuran (L5) did not form chelating palladium complexes, owing to its large natural bite angle of 138 degree.The crystal structures of L6, *2.5CH2Cl2 1, *4CH2Cl2 2, *2CH2Cl2 4 and 5 have been determined.The similarity of electronic effects induced by the free diphosphines was demonstrated by MOPAC calculations.The geometries of the ligands, however, were most accurately predicted by molecular mechanics (MM2) calculations for the diphosphines, and MNDO for L6.The largest P-Pd-P angle in the zerovalent palladium complexes was found to be 104.6 degree.A further increase in the natural bite angle of the ligand results in elongation of the Pd-P bond length in the complex rather than enlargement of the P-Pd-P bite angle.The ligand L6 assumed a bite angle of 99.5(2) degree in complex 5, which is considerably smaller than its calculated value of 117 degree.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.166330-10-5, Name is (Oxybis(2,1-phenylene))bis(diphenylphosphine), molecular formula is C36H28OP2. In a Article,once mentioned of 166330-10-5, SDS of cas: 166330-10-5

Seven luminescent copper(I) complexes bearing four-coordinate N-heterocyclic carbene (NHC) ligands with varying electron-withdrawing substituents including ?CF3, ?CN, ?COCH3, and ?CHO groups at the pyridine ring part of the carbene are reported in this study. P1-P4 without the methyl group show better light absorption in low-energy region compared with P5-P7 with the methyl group at the alpha-position of the pyridine ring. The emitting state of all the complexes is regarded as the 3MLCT/3LLCT character. P1-P4 exhibit the emission maximum in the range of 537?547 nm with the photoluminescence quantum yields (PLQY) of 12.7?21.9% in PMMA films and excited state lifetimes (tau) of 14.7?22.6 mus. The emission wavelengths of P5-P7 are blue-shifted to 505?513 nm compared with those of P1-P4, showing the higher PLQY of 38.0?57.3% and longer tau of 36.2?84.8 mus. Theoretical calculations were used to rationalize the photophysical properties.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 166330-10-5, Name is (Oxybis(2,1-phenylene))bis(diphenylphosphine), molecular formula is C36H28OP2. In a Article,once mentioned of 166330-10-5, Product Details of 166330-10-5

We developed a method to improve the performance of the copper phthalocyanine (CuPc)/fullerene (C60) organic solar cells (OSCs) by doping CuPc with a long triplet lifetime material. By doping [Cu(bis[2-(diphenylphosphino)phenyl]ether)(benzo[i]dipyrido[3,2-a:2?,3?-c]phenazine)]BF4 (CuDB) into CuPc, the enhanced short-circuit current density (JSC) of 6.213 mA/cm2, open-circuit voltage (VOC) of 0.39 V and a peak power conversion efficiency (PCE) of 0.92% compared to 0.79% of the standard CuPc/C60 OSCs are achieved under 1 sun AM 1.5 G illumination at an intensity of 100 mW/cm2. The performance improvement is mainly attributed to the long triplet lifetime of CuDB (tau = 70.05 mus) which leads to more effective exciton dissociation.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate