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Synthesis, crystal structures and photo- and electro-luminescence of copper(I) Complexes containing electron-transporting diaryl-1,3,4-oxadiazole

Two mononuclear Cu(I) complexes based on 2-(2-pyridyl)benzimidazolyl derivative ligand containing electron-transporting 1,3,4-oxadiazole group (L), [Cu(L)(PPh3)2](BF4) and [Cu(L)(DPEphos)] (BF4), where L=1-(4-(5-(4-tert-butylphenyl)-1,3,4-oxadiazol-2-yl) benzyl)-2-(pyridin-2-yl)benzimidazole and DPEphos=bis[2-(diphenylphosphino) phenyl]ether, have been successfully synthesized and characterized. The X-ray crystal structure analyses of the ligand L and the complex [Cu(L)(PPh 3)2](BF4) were described. The photophysical properties of the complexes were examined by using UV-vis, photoluminescence spectroscopic analysis. The doped light-emitting devices using the Cu(I) complexes as dopants were fabricated. With no electron transporting layers employed in the devices, yellow electroluminescence from Cu(I) complexes were observed. The devices based on the complex [Cu(L)(DPEphos)](BF4) possess better performance as compared with the devices fabricated by the complex [Cu(L)(PPh3)2](BF4). The devices with the structure of ITO/MoO3 (2 nm)/NPB (40 nm)/CBP:[Cu(L)(DPEphos)] (BF4) (8 wt%, 30 nm)/BCP (30 nm)/LiF (1 nm)/Al (150 nm) exhibit a maximum efficiency of 3.04 cd/A and a maximum brightness of 4,758 cd/m 2.

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Reference£º
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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Luminescence Thermochromism of Gold(I) Phosphane?Iodide Complexes: A Rule or an Exception?

A series of gold(I) iodide complexes 1?11 have been prepared from di-, tri-, and tetraphosphane ligands. Crystallographic studies reveal that the di- (1?7) and tetrametallic (11) compounds feature linearly coordinated gold(I) ions with short aurophilic contacts. Their luminescence behavior is determined by the combined influence of the phosphane properties, metal?metal interaction, and intermolecular lattice-defined interactions. The proposed variable contribution of 3(X+M)-centered (X=halogen; M=metal) and 3XLCT (halogen to ligand charge transfer) electronic transitions into the lowest lying excited state, which is influenced by supramolecular packing, is presumably responsible for the alteration of room-temperature emission color from green (lambda=545 nm, for 11) to near-IR (lambda=698 nm, for 2). Dinuclear compounds 6 and 7 exhibit distinct luminescence thermochromism with a blueshift up to 5750 cm?1 upon cooling. Such dramatic change of emission energy is assigned to the presence of two coupled triplet excited states of 3pipi* and 3(X+M)C/3XLCT nature, the presence of which depends on both molecular structure and the crystal lattice arrangement.

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Reference£º
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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Dynamic topomerization of Cu(i)-complexed pseudorotaxanes

Dynamic molecular motions resulting from the folding of a flexible macrocyclic component in a Cu(i)-complexed pseudorotaxane have been evidenced by variable temperature NMR experiments. The proposed conformational changes are also supported by the X-ray crystal structures of the compounds and computational studies.

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Reference£º
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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Recent advances in organic light-emitting devices comprising copper complexes: A realistic approach for low-cost and highly emissive devices?

The past decades have driven a great deal of interest for developing low-cost electroluminescent devices. In this aim, highly emissive phosphors based on Earth-abundant metals and presenting the advantage of environment-benignancy are actively researched. Based on these requirements, copper(I) complexes have been identified as favorable candidates that could advantageously replace the well-established iridium(III) complexes.

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Reference£º
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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Synthesis, crystal structures and photo- and electro-luminescence of copper(I) Complexes containing electron-transporting diaryl-1,3,4-oxadiazole

Two mononuclear Cu(I) complexes based on 2-(2-pyridyl)benzimidazolyl derivative ligand containing electron-transporting 1,3,4-oxadiazole group (L), [Cu(L)(PPh3)2](BF4) and [Cu(L)(DPEphos)] (BF4), where L=1-(4-(5-(4-tert-butylphenyl)-1,3,4-oxadiazol-2-yl) benzyl)-2-(pyridin-2-yl)benzimidazole and DPEphos=bis[2-(diphenylphosphino) phenyl]ether, have been successfully synthesized and characterized. The X-ray crystal structure analyses of the ligand L and the complex [Cu(L)(PPh 3)2](BF4) were described. The photophysical properties of the complexes were examined by using UV-vis, photoluminescence spectroscopic analysis. The doped light-emitting devices using the Cu(I) complexes as dopants were fabricated. With no electron transporting layers employed in the devices, yellow electroluminescence from Cu(I) complexes were observed. The devices based on the complex [Cu(L)(DPEphos)](BF4) possess better performance as compared with the devices fabricated by the complex [Cu(L)(PPh3)2](BF4). The devices with the structure of ITO/MoO3 (2 nm)/NPB (40 nm)/CBP:[Cu(L)(DPEphos)] (BF4) (8 wt%, 30 nm)/BCP (30 nm)/LiF (1 nm)/Al (150 nm) exhibit a maximum efficiency of 3.04 cd/A and a maximum brightness of 4,758 cd/m 2.

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Reference£º
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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Heteroleptic Copper(I) Pseudorotaxanes Incorporating Macrocyclic Phenanthroline Ligands of Different Sizes

A series of copper(I) pseudorotaxanes has been prepared from bis[2-(diphenylphosphino)phenyl] ether (POP) and macrocyclic phenanthroline ligands with different ring sizes (m30, m37, and m42). Variable-temperature studies carried out on the resulting [Cu(mXX)(POP)]+ (mXX = m30, m37, and m42) derivatives have revealed a dynamic conformational equilibrium due to the folding of the macrocyclic ligand. The absorption and luminescence properties of the pseudorotaxanes have been investigated in CH2Cl2. They exhibit metal-to-ligand charge-transfer emission with photoluminescence quantum yields (PLQYs) in the range 20-30%. The smallest system [Cu(m30)(POP)]+ shows minimal differences in spectral shape and position compared to its analogues, suggesting a slightly distorted coordination environment. PLQY is substantially enhanced in poly(methyl methacrylate) films (?40?45%). The study of emission spectra and excited-state lifetimes in powder samples as a function of temperature (78-338 K) reveals thermally activated delayed fluorescence, with sizable differences in the singlet-triplet energy gap compared to the reference compound [Cu(dmp)(POP)]+ (dmp = 2,9-dimethyl-1,10-phenanthroline) and within the pseudorotaxane series. The system with the largest ring ([Cu(m42)(POP)]+) has been tested as emissive material in OLEDs and affords bright green devices with higher luminance and greater stability compared to [Cu(dmp)(POP)]+, which lacks the macrocyclic ring. This highlights the importance of structural factors in the stability of electroluminescent devices based on Cu(I) materials.

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Reference£º
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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Facile synthesis of benzonitrile/nicotinonitrile based s-triazines as new potential antimycobacterial agents

A common strategy to synthesize 4/6-(4-(4-methylpiperazin-1-yl)-6-(4-(4- oxo-2-phenylthiazolidin-3-yl)phenyl)-1,3,5-triazin-2-yloxy)benzonitriles/ nicotinonitriles was developed by applying an efficient palladium-catalyzed C-C Suzuki coupling. Moreover, the synthesized compounds were also tested for their in vitro antimycobacterial activity against Mycobacterium tuberculosis H 37Rv using BACTEC MGIT and Lowenstein-Jensen MIC methods. Several compounds displayed profound antimycobacterial activity in combination with low toxicity towards mammalian cells. The best results were observed amongst the nicotinonitrile substituted s-triazine analogs and it could be a potential starting point to develop new lead compounds in the fight against M. tuberculosis H37Rv. The newly synthesized compounds were characterized by IR, 1H NMR, 13C NMR, MS and elemental analysis.

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Reference£º
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 New Highly Efficient Amine-Free and Peroxide-Free Redox System for Free Radical Polymerization under Air with Possible Light Activation

Efficient redox initiating systems for radical polymerizations under air usually show some severe drawbacks such as handling and toxicity of the oxidizing agent (peroxides, persulfates, peroxidiphosphates, disulfides, etc.), toxicity of the reducing agent (aromatic amines such as 4-N,N-trimethylaniline), and more generally a low top surface conversion due to high oxygen inhibition. The originality of the proposed paper relies on the development of new redox initiating systems for the polymerization of (meth)acrylate monomers that does not contain any hazardous compound (no peroxide) and is amine-free (low toxicology issues). And these new systems that possess the advantages of redox-initiated polymerization (possibility to cure thick samples) can also be photoactivated in order to have a faster and better curing of the surface of the sample (advantages of the photopolymerization to overcome the oxygen inhibition). The light activations presented in this work have been done with light-emitting diodes (LEDs) as they have a low energy consumption and are safer to the user than UV light. Two wavelengths have been used: 405 nm (in the blue range of the spectrum) and 780 nm (in the near-infrared) showing the versatility of these new photo/redox initiating systems. In particular, the reactivity in the near-IR (not related to any heating of the sample) is a very original result. In addition with the presentation of the performance of the new systems in polymerization and photoactivated polymerization, a full analysis of the chemical mechanisms and species involved has been performed. Remarkably, the new proposed Cu(acac)2/2dppba system is also able to overcome the oxygen inhibition for free radical redox (photo)polymerization.

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Reference£º
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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PROCESS FOR PREPARING BENZIMIDAZOLE COMPOUNDS

Provided are methods for the synthesis of heterocyclic compounds such as benzimidazole carboxylic acid core structures having Formula Ia-1 and their synthetic intermediates:wherein Z, X1 , X2 , X5 , R2 and R10 are as defined herein. Compounds of Formula Ia-1 and their synthetic intermediatescan be used to prepare heterocyclic derivatives such as benzimidazole derivatives

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Reference£º
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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Oxygen gas sensing by luminescence quenching in crystals of Cu(xantphos)(phen)+ complexes

We have shown that crystals of the highly emissive copper(I) compounds [Cu(POP)(dmp)]tfpb, [Cu(xantphos)(dmp)]tfpb, [Cu(xantphos)(dipp)]tfpb, and [Cu(xantphos)(dipp)]pftpb, (where POP = bis[2-(diphenylphosphino)phenyl]ether; xantphos = 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; dmp = 2,9-dimethyl-1,10-phenanthroline; dipp = 2,9-diisopropyl-1,10-phenanthroline (dipp); tfpb- = tetrakis(bis-3,5-trifluoromethylphenylborate); and pftpb = tetrakis(pentfluorophenyl)borate) are oxygen gas sensors. The sensing ability correlates with the amount of void space calculated from the crystal structures. The compounds exhibit linear Stern-Volmer plots with reproducible KSV constants from sample to sample; these results reinforce the observations that the sensing materials are crystalline and the sensing sites are homogeneous within the crystals. The long lifetime (?30 mus), high emission quantum yield (beta = 0.66), appreciable KSV value (5.65), and very rapid response time (51 ms for the 95% return constant) for [Cu(xantphos)(dmp)]tfpb are significantly better than those for the [Cu(NN) 2]tfpb complexes studied previously and compare favorably with [Ru(4,7-Me2phen)3](tfpb)2, (KSV = 4.76; 4,7-Me2phen = 4,7-dimethyl-1,10- phenanthroline). The replacement of precious metals (like Ru or Pt) with copper may be technologically significant and the new compounds can be synthesized in one or two steps from commercially available starting materials. The strictly linear Stern-Volmer behavior observed for these systems and the absence of a polymer matrix that might cause variability in sensor to sensor sensitivity may allow a simple single-reference point calibration procedure, an important consideration for an inexpensive onetime limited use sensor that could be mass produced.

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Reference£º
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