Search results for "Effects"
showing 10 items of 2634 documents
Self-assembly in surfactant-based mixtures driven by acid–base reactions: bis(2-ethylhexyl) phosphoric acid–n-octylamine systems
2013
Structural and dynamic features of bis(2-ethylhexyl) phosphoric acid (HDEHP)-n-octylamine (NOA) mixtures as a function of the NOA mole fraction (X-NOA) have been investigated by SAXS, WAXS, IR, dielectric spectroscopy and polarized optical microscopy. In the 0 <= X-NOA < 0.5 range, mixtures are transparent liquids, while the abrupt formation of a waxy solid characterized by an hexagonal bidimensional structure occurs at X-NOA = 0.5. Such a composition-induced phase transition results from the synergetic effect of the progressive increase in number density of ordered HDEHP-NOA nanodomains with X-NOA. Mainly driven by an HDEHP to NOA proton transfer, the increase of structural order with X-NO…
Modular P-Chirogenic Aminophosphane-Phosphinite Ligands for Rh-Catalyzed Asymmetric Hydrogenation: A New Model for Prediction of Enantioselectivity
2007
An original series of P-chirogenic aminophosphane-phosphinite (AMPP) ligands has been synthesized from (+)- or(–)-ephedrine in 23 to 61 % overall yields by a versatile three-step methodology. The AMPP ligands, bearing either one or two P-chirogenic centers, were used in the form of rhodium complexes for the catalyzed hydrogenation of α-acetamidocinnamate as a test reaction. Notably, even with AMPP ligands all derived from (+)-ephedrine, variation of the substituent on a P-center allowed the phenylalanine derivatives to be obtained in either (S) or (R) absolute configurations, with ee values ranging from 99 % (S) to 88 % (R). The asymmetric induction was analyzed with the aid of X-ray struct…
Can Green Dimethyl Carbonate Synthesis be More Effective? A Catalyst Recycling Study Benefiting from Experimental Kinetics and DFT Modeling
2014
Dibutyldimethoxystannanes are known to catalyze the reaction between carbon dioxide and methanol leading to dimethyl carbonate. Despite similarities between din-butyl- and ditert-butyldimethoxystannane, the recycled complexes have different structural features. In the din-butyl series, a decatin(IV) complex has been characterized and is less active than the stannane precursor. Kinetic experiments likely indicate that all the tin centers are not active, which is confirmed in comparing with the related dinuclear 1,3-dimethoxytetran-butyldistannoxane complex. In the ditert-butyl series, the tritin(IV) complex isolated upon recycling features the steric effect of bulky tBu ancillary ligands. In…
Ag44(EBT)26(TPP)4Nanoclusters With Tailored Molecular and Electronic Structure
2021
Although atomically precise metalloid nanoclusters (NCs) of identical size with distinctly different molecular structures are highly desirable to understand the structural effects on the optical and photophysical properties, their synthesis remains highly challenging. Herein, we employed phosphine and thiol capping ligands featuring appropriate steric effects and synthesized a charge-neutral Ag NC with the formula Ag44 (EBT)26 (TPP)4 (EBT: 2-ethylbenzenethiolate; TPP: triphenylphosphine). The single-crystal X-ray structure reveals that this NC has a hollow metal core of Ag12 @Ag20 and a metal-ligand shell of Ag12 (EBT)26 (TPP)4 . The presence of mixed ligands and long V-shaped metal-ligand …
Phosphane tuning in heteroleptic [Cu(N^N)(P^P)]+ complexes for light-emitting electrochemical cells
2019
The synthesis and characterization of five [Cu(P^P)(N^N)][PF 6 ] complexes in which P^P = 2,7-bis( tert -butyl)-4,5-bis(diphenylphosphino)-9,9-dimethylxanthene ( t Bu 2 xantphos) or the chiral 4,5-bis(mesitylphenylphosphino)-9,9-dimethylxanthene (xantphosMes 2 ) and N^N = 2,2'-bipyridine (bpy), 6-methyl-2,2'-bipyridine (6-Mebpy) or 6,6'-dimethyl-2,2'-bipyridine (6,6'-Me 2 bpy) are reported. Single crystal structures of four of the compounds confirm that the copper(I) centre is in a distorted tetrahedral environment. In [Cu(xantphosMes 2 )(6-Mebpy)][PF 6 ], the 6-Mebpy unit is disordered over two equally populated orientations and this disorder parallels a combination of two dynamic processe…
Impact of the use of sterically congested Ir(III) complexes on the performance of light-emitting electrochemical cells
2018
International audience; The synthesis, structural and optoelectronic characterization of a family of sterically congested cyclometalated cationic Ir(iii) complexes of the form [Ir(C^N)2(dtBubpy)]PF6 (with dtBubpy = 4,4′-di-tert-butyl-2,2′-bipyridine and C^N = a cyclometalating ligand decorated at the 4-position of the pyridine ring and/or the 3-position of the phenyl ring with a range of sterically bulky substituents) are reported. This family of complexes is compared to the unsubstituted analogue complex R1 bearing 2-phenylpyridinato as cyclometalating ligand. The impact of sterically bulky substituents on the C^N ligands on both the solid state photophysics and light-emitting electrochemi…
Modeling Supramolecular Polymerization: The Role of Steric Effects and Hydrophobic Interactions
2019
We present a combined experimental–simulation study of self-assembly into one-dimensional filaments. Experimentally, we study amphiphilic AuI-metallopeptides in neutral aqueous media. Our model foc...
Molecular Mechanisms Controlling the Self-Assembly Process of Polyelectrolyte Multilayers
1998
The distance dependent interaction between polyelectrolyte-covered mica surfaces in aqueous solution was investigated with the surface forces apparatus. We find the following: (i) The surface charge changes sign, when an oppositely charged polyelectrolyte from a concentrated polyelectrolyte solution is adsorbed. (ii) Tails and loops of the adsorbed polyions dangle into the bulk phase, inducing a small steric force. If polycations and poyanions are adsorbed on top of each other, a strong short range attractive force is seen due to ion-pair formation after crossing a large repulsive electrostatic/steric barrier. (iii) Obviously, after polyelectrolyte adsorption, there are still nonoccupied b…
Local control of antibody binding to hapten-presenting interfaces: Steric and electrostatic interaction
1991
The binding of labeled antibodies to hapten substituted monolayers at the air/water interface has been studied by means of fluorescence microscopy. Haptens with various spacer lengths between the epitope and a hydrocarbon chain, anchoring the molecule to the interface, have been synthesized. With DMPC,a unspecific binding has been shown to predominate over specific binding due to electrostatic interactions. At high surface pressures the bound antibody is detached because of steric interference with the lipid head groups. Due to a reduction of electrostatic interactions, no unspecific binding is observed to monolayers of cholesterol, which carries a small dipole moment. Mixed monolayers of c…
Introducing a 1,1-diphenylethylene analogue for vinylpyridine: anionic copolymerisation of 3-(1-phenylvinyl)pyridine (m-PyPE)
2021
3-(1-Phenylvinyl)pyridine (m-PyPE), prepared by Wittig reaction from the readily available 3-benzoylpyridine, represents a structural analog of 1,1-diphenylethylene (DPE), one phenyl group being replaced by pyridine. The suitability of m-PyPE for the copolymerisation with vinylpyridine is reflected by the 13C NMR shifts of the β-carbon of 2-vinylpyridine (2-VP; 118.32 ppm) and m-PyPE (115.83 ppm, measured in CDCl3), which possess predictive character for carbanionic copolymerisation. In analogy to DPE and its manifold reported derivatives, carbanionic homopolymerisation of m-PyPE was not possible, due to its steric bulk. Copolymers of 2-VP and m-PyPE with varied composition have been synthe…