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A novel cuprous complex bearing two functional parts, i.e. a luminophoric part and a structural part, exhibits distinct luminescence responses to a variety of volatile organic compounds of different polarities in the solid state.

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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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Five mononuclear copper(I) complexes and one dinuclear silver(I) phosphine complex containing the bispyridylpyrrole ligand were synthesized and structurally characterized. Treatment of CuCl and the deprotonated bispyridylpyrrole ligand with bis(phosphine) ligands afforded the copper(I) complexes [(PDPH)Cu(XANTPhos)] (1), [(PDPH)Cu(DPEPhos)] (2), [(PDPBr)Cu(XANTPhos)] (3) and [(PDPBr)Cu(DPEPhos)] (4), while addition of two equivalences of PPh3 gave [(PDPBr)Cu(PPh3)2] (5), where PDPH- = 2,5-bis(2-pyridyl)pyrrole, PDPBr- = 2,5-bis(6?-bromo-2?-pyridyl)-pyrrole, XANTPhos = 9,9-di-methyl-4,5-bis(diphenylphosphino)xanthene, DPEPhos = oxydi-2,1-phenylene)bis-diphenylphosphine. Reaction of PDPBr- with AgOTf and DPEPhos yielded the dinuclear silver(I) complex [(PDPBr)Ag2(DPEPhos)](OTf) (6). All of these complexes were fully characterized on the basis of IR spectra, 1H and 31P NMR spectra, elements analysis, UV-Vis spectra and X-ray single crystal diffraction analysis. The photophysical properties of these complexes were also studied.

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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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Six heteroleptic cuprous complexes, [L1Cu(PPh3) 2](BF4) (1a), [L1Cu(DPEphos)](BF4) (1b), [L2Cu(PPh3)2](BF4) (2a), [L2Cu-(DPEphos)](BF4) (2b), [L3Cu(PPh 3)2](BF4) (3a), and [L3Cu-(DPEphos)] (BF4) (3b) {L1 = diphenyl(2-pyridyl)phosphane oxide, L2 = diphenyl(8-quinolyl)phosphane oxide, L3 = diphenyl(2-pyridylmethyl)phosphane oxide, DPEphos = bis[2-(diphenylphosphanyl) phenyl] ether}, were prepared and fully characterized. The electronic absorption spectra and quantum chemical calculations indicate that the lowest excited states of these complexes can be assigned to the metalto-ligand charge transfer (MLCT) transition. In poly(methyl methacrylate) (PMMA) films, these complexes exhibit bluegreen to orange emissions with long lifetimes ranging from 7.5 to 28.6 mus. With wide energy-band gaps of 3.50 and 3.28 eV, complexes 3a and 3b emit efficiently in 20 wt.-% PMMA films with photoluminescence quantum efficiencies of 0.69 and 0.72, and emission maxima at 477 nm and 495 nm, respectively. Electroluminescent devices were fabricated with these N,O-based CuI complexes as emitters. The best device performance, with a peak current efficiency of 4.9 cd/A, was obtained for 3b.

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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 ionic (1a and 1b) and two neutral (2a and 2b) Cu(i) complexes containing an un-deprotonated or a deprotonated nitrogen ligand {2-(4-methyl phenyl) imidazole[4,5-f]-1,10-phenanthroline, MHPIP} and different phosphine ligands (bis[2-(diphenylphosphino) phenyl]ether and PPh3) have been synthesized and characterized by elemental analysis, 1H NMR spectroscopy and X-ray crystallography (1b, 2a and 2b). The complexes adopt a distorted tetrahedral geometry constructed by MHPIP (or MPIP-) and phosphine ligands. The emission spectra show that the ionic complexes exhibit almost ignorable luminescence. However, the deprotonation of the nitrogen ligand makes the neutral complexes exhibit orange or yellow emission both in solution and solid-powder states. Considering the different luminous characters of the neutral complexes, density functional theory (DFT) calculations have been performed at the B3LYP/6-31G?? level to provide information about the impact of phosphine ligands on the frontier orbital.

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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 series of chelating phosphine ligands, which contain bidentate P2 (bis[(2-diphenylphosphino)phenyl] ether, DPEphos; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, Xantphos; 1,2-bis(diphenylphosphino)benzene, dppb), tridentate P3 (bis(2-diphenylphosphinophenyl)phenylphosphine), and tetradentate P4 (tris(2-diphenylphosphino)phenylphosphine) ligands, was used for the preparation of the corresponding dinuclear [M(mu2-SCN)P2]2 (M = Cu, 1, 3, 5; M = Ag, 2, 4, 6) and mononuclear [CuNCS(P3/P4)] (7, 9) and [AgSCN(P3/P4)] (8, 10) complexes. The reactions of P4 with silver salts in a 1:2 molar ratio produce tetranuclear clusters [Ag2(mu3-SCN)(t-SCN)(P4)]2 (11) and [Ag2(mu3-SCN)(P4)]22+ (12). Complexes 7-11 bearing terminally coordinated SCN ligands were efficiently converted into derivatives 13-17 with the weakly coordinating -SCN:B(C6F5)3 isothiocyanatoborate ligand. Compounds 1 and 5-17 exhibit thermally activated delayed fluorescence (TADF) behavior in the solid state. The excited states of thiocyanate species are dominated by the ligand to ligand SCN ? pi(phosphine) charge transfer transitions mixed with a variable contribution of MLCT. The boronation of SCN groups changes the nature of both the S1 and T1 states to (L + M)LCT d,p(M, P) ? pi(phosphine). The localization of the excited states on the aromatic systems of the phosphine ligands determines a wide range of luminescence energies achieved for the title complexes (lambdaem varies from 448 nm for 1 to 630 nm for 10c). The emission of compounds 10 and 15, based on the P4 ligand, strongly depends on the solid-state packing (lambdaem = 505 and 625 nm for two crystalline forms of 15), which affects structural reorganizations accompanying the formation of electronically excited states.

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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 process for the production of 4-acetoxybutyraldehyde is described. The process comprises reacting allyl acetate with a mixture of carbon monoxide and hydrogen in the presence of a solvent and a catalyst comprising a rhodium complex and a diphosphine. The diphoshine is a substituted or unsubstituted 2,2?-bis(dihydrocarbylphosphino)diphenyl ether. The process gives a high ratio of 4-acetoxybutyraldehyde:3-acetoxy-2-methylpropionaldehyde.

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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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We report the synthesis and characterisation of new examples of meso-hydroxynickel(II) porphyrins with 5,15-diphenyl and 10-phenyl-5,15-diphenyl/diaryl substitution. The OH group was introduced by using carbonate or hydroxide as nucleophile by using palladium/phosphine catalysis. The NiPor-OHs exist in solution in equilibrium with the corresponding oxy radicals NiPor-O.. The 15-phenyl group stabilises the radicals, so that the 1H NMR spectra of {NiPor-OH} are extremely broad due to chemical exchange with the paramagnetic species. The radical concentration for the diphenylporphyrin analogue is only 1 %, and its NMR line-broadening was able to be studied by variable-temperature NMR spectroscopy. The EPR signals of NiPor-O. are consistent with somewhat delocalised porphyrinyloxy radicals, and the spin distributions calculated by using density functional theory match the EPR and NMR spectroscopic observations. Nickel(II) meso-hydroxy-10,20-diphenylporphyrin was oxidatively coupled to a dioxo-terminated porphodimethene dyad, the strongly red-shifted electronic spectrum of which was successfully modelled by using time-dependent DFT 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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The reaction of equimolar amounts of AgI and the ligand bis(2-(diphenylphosphino)phenyl)ether (DPEphos) in the ionic liquid [NMe(n-Bu)3]2[N(Tf)2] yields the dinuclear complex Ag2I2(DPEphos)2. Herein, each silver atom is coordinated by two iodide anions and two DPEphos ligands, resulting in a distorted tetrahedral coordination. Moreover, Ag-Ag interaction (293.7 pm) is observed and represents the shortest bonding observed for dinuclear silver phosphine complexes.

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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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There is a need for high-quality screening collections that maximise hit rate and minimise the time taken in lead optimisation to derive a candidate drug. Identifying and accessing molecules that meet these criteria is a challenge. Within central nervous system (CNS)-focused drug discovery, this challenge is heightened by the requirement for lead compounds to cross the blood?brain barrier. Herein, we demonstrate use of a multiparameter optimisation tool to prioritise the synthesis of molecular scaffolds that, when subsequently decorated, yield screening compounds with experimentally determined properties that align with CNS lead generation needs. Prospective use of this CNS Lead Multiparameter Optimisation (MPO) scoring protocol can guide the further development of novel synthetic methodologies to access CNS-relevant and lead-like chemical space.

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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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An effective Pd(0)-catalyzed hydrocarboxylation of enimides with formic acid in the presence of a catalytic amount of HCOOPh is described. A variety of beta-amino acid derivatives are obtained in good yields with high regioselectivities without using external toxic CO gas.

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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