Search results for "phosphine"
showing 10 items of 618 documents
High Photoluminescence Quantum Yields in Organic Semiconductor-Perovskite Composite Thin Films.
2017
One of the obstacles towards efficient radiative recombination in hybrid perovskites is a low exciton binding energy, typically in the orders of tens of meV. It has been shown that the use of electron-donor additives can lead to a substantial reduction of the non-radiative recombination in perovskite films. Herein, the approach using small molecules with semiconducting properties, which are candidates to be implemented in future optoelectronic devices, is presented. In particular, highly luminescent perovskite-organic semiconductor composite thin films have been developed, which can be processed from solution in a simple coating step. By tuning the relative concentration of methylammonium l…
Anticancer Agents: Does a Phosphonium Behave Like a Gold(I) Phosphine Complex? Let a “Smart” Probe Answer!
2015
Gold phosphine complexes, such as auranofin, have been recognized for decades as antirheumatic agents. Clinical trials are now underway to validate their use in anticancer or anti-HIV treatments. However, their mechanisms of action remain unclear. A challenging question is whether the gold phosphine complex is a prodrug that is administered in an inactive precursor form or rather that the gold atom remains attached to the phosphine ligand during treatment. In this study, we present two novel gold complexes, which we compared to auranofin and to their phosphonium analogue. The chosen ligand is a phosphine-based smart probe, whose strong fluorescence depends on the presence of the gold atom. …
New concepts in multidentate ligand chemistry: effects of multidentarity on catalytic and spectroscopic properties of ferrocenyl polyphosphines.
2008
This tutorial review devoted to ligand chemistry deals with the design and properties of ferrocenyl polyphosphines, an original class of multidentate ligands. The development of a varied library of ferrocenyl tetra-, tri- and diphosphine ligands is reviewed. The multidentate nature of these species has led to unique spectroscopic and catalytic properties, in which the spatial proximity of phosphorus atoms is crucial. Regarding their catalytic applications, the key issues of catalyst longevity and ultralow catalyst loadings are discussed. Another part is concerned with fundamental advances gained in physical chemistry for structure elucidation by the study of the intriguing “through-space” N…
Thioetherification of Chloroheteroarenes: A Binuclear Catalyst Promotes Wide Scope and High Functional-Group Tolerance
2014
A constrained binuclear palladium catalyst system affords selective thioetherification of a wide range of functionalized arenethiols with chloroheteroaromatic partners with the highest turnover numbers (TONs) reported to date and tolerates a large variety of reactive functions. The scope of this system includes the coupling of thiophenols with six- and five-membered 2-chloroheteroarenes (i.e., functionalized pyridine, pyrazine, quinoline, pyrimidine, furane, and thiazole) and 3-bromoheteroarenes (i.e., pyridine and furane). Electron-rich congested thiophenols and fluorinated thiophenols are also suitable partners. The coupling of unprotected amino-2-chloropyridines with thiophenol and the s…
Luminescent alkynyl-gold(i) coumarin derivatives and their biological activity
2013
The synthesis and characterization of three propynyloxycoumarins are reported in this work together with the formation of three different series of gold(i) organometallic complexes. Neutral complexes are constituted by water soluble phosphines (PTA and DAPTA) which confer water solubility to them. The X-ray crystal structure of 7-(prop-2-in-1-yloxy)-1-benzopyran-2-one and its corresponding dialkynyl complex is also shown and the formation of rectangular dimers for the gold derivative in the solid state can be observed. A detailed analysis of the absorption and emission spectra of both ligands and complexes allows us to attribute the luminescent behaviour to the coumarin organic ligand. More…
Congested ferrocenyl polyphosphanes bearing electron-donating or electron-withdrawing phosphanyl groups: assessment of metallocene conformation from …
2011
International audience; The synthesis of novel substituted cyclopentadienyl salts that incorporate both a congested branched alkyl group (tert-butyl, (triphenyl)methyl, or tri(4-tert-butyl)phenylmethyl) and a phosphanyl group is reported. The introduction of either electron-withdrawing or electron-donating substituents (furyl, i-propyl, cyclohexyl, tert-butyl) on P atoms was generally achieved in high yield. The modular synthesis of ferrocenyl polyphosphanes from an assembly of these cyclopentadienyl salts was investigated, leading to the formation of new triphosphanes (denoted as 9-12) and diphosphanes (denoted as 14-16). The resulting phosphanes are not sensitive to air or moisture, even …
Stereoselective Synthesis of P-Chirogenic Dibenzophosphole-Boranes via Aryne Intermediates
2012
A new aryne-mediated tandem cross-coupling/P-cyclization sequence starting from tertiary phosphine-boranes and 1,2-dibromobenzenes is reported. P-chirogenic dibenzophospholes become accessible in a regio-, chemo-, and diastereoselective way.
Cubane-Type Mo3FeS44+,5+ Complexes Containing Outer Diphosphane Ligands: Ligand Substitution Reactions, Spectroscopic Studies, and Electronic Structu…
2012
A general protocol to access Mo(3)FeS(4)(4+) clusters selectively modified at the Fe coordination site is presented starting from the all-chlorine Mo(3)(FeCl)S(4)(dmpe)(3)Cl(3) (1) [dmpe = 1,2-bis(dimethylphosphane-ethane)] cluster and tetrabutylammonium salts (n-Bu(4)NX) (X = CN(-), N(3)(-), and PhS(-)). Clusters Mo(3)(FeX)S(4)(dmpe)(3)Cl(3) [X = CN(-) (2), N(3)(-) (3), and PhS(-) (4)] are prepared in high yield, and comparison of geometric and redox features upon modification of the coordination environment at the Fe site at parity of ligands at the Mo sites is also presented. The existence of the cubane-type Mo(3)FeS(4)(4+,5+) redox couple is demonstrated by cyclic voltammetry and for co…
Ligand-Stabilized Au13Cux (x = 2, 4, 8) Bimetallic Nanoclusters: Ligand Engineering to Control the Exposure of Metal Sites
2013
Three novel bimetallic Au-Cu nanoclusters stabilized by a mixed layer of thiolate and phosphine ligands bearing pyridyl groups are synthesized and fully characterized by X-ray single crystal analysis and density functional theory computations. The three clusters have an icosahedral Au13 core face-capped by two, four, and eight Cu atoms, respectively. All face-capping Cu atoms in the clusters are triply coordinated by thiolate or pyridyl groups. The surface ligands control the exposure of Au sites in the clusters. In the case of the Au13Cu8 cluster, the presence of 12 2-pyridylthiolate ligands still leaves open space for catalysis. All the 3 clusters are 8-electron superatoms displaying opti…
Organometallic Oligomers Based on Bis(arylacetylide)bis(P-chirogenic phosphine)platinum(II) Complexes: Synthesis and Photonic Properties
2013
A series of P-chirogenic oligomers of the type (-C≡C-aryl-C≡C-PtL2-)n [L = (R)- and (S)-P(Ph)(iPr)(C17H35); aryl = 1,4-benzene, 2,1,3-benzothiadiazole] along the corresponding achiral analogues (L = PBu3) and model complexes PhC≡CPtL2C≡CPh were prepared from the ephedrine strategy and were fully characterized [(1)H, (31)P NMR; IR; small-angle X-ray scattering (SAXS); gel permeation chromatography (GPC); thermal gravimetric analysis (TGA); circular dichroism, UV-vis, and luminescence spectroscopy; photophysics, and degree of anisotropy measurements]. From the CD measurements, the chiral environment of the phosphine ligands is modestly felt by the aryl moieties. Concurrently, the TGA shows th…