Search results for "Phenyl group"

Tuning the Electronic Properties of Nonplanar exTTF-Based Push–Pull Chromophores by Aryl Substitution

2012

International audience; A new family ofπ-extended tetrathiafulvalene (exTTF) donor−acceptorchromophores has been synthesized by [2 + 2] cycloaddition of TCNE with exTTF-substituted alkynes and subsequent cycloreversion. X-ray data and theoretical calculations,performed at the B3LYP/6-31G**level, show that the new chromophores exhibit highlydistorted nonplanar molecular structures with largely twisted 1,1,4,4-tetracyanobuta-1,3-diene (TCBD) units. The electronic and optical properties, investigated by UV/visspectroscopy and electrochemical measurements, are significantly modified when theTCBD acceptor unit is substituted with a donor phenyl group, which increases the twistingof the TCBD unit…

ENANTIOSELECTIVE REDUCTION OF PROCHIRAL KETONES PROMOTED BY AMINO AMIDE RUTHENIUM COMPLEXES: A DFT STUDY

2021

International audience; The origin of enantioselectivity in the reaction of chiral Ru amino amide complexes in the asymmetric transfer hydrogenation of acetophenone was investigated using DFT calculations. For the most stable active catalysts, the full free energy profiles for the reaction were calculated according to the concerted hydrogen transfer mechanism. We succeeded in reproducing the experimentally observed enantioselectivity for the studied Ru amino amide complexes. Our results indicate that the high enantioselectivity can be explained by a stabilizing CH-π interaction existing between the phenyl group of acetophenone and the aromatic substituent of the catalyst, which plays a sign…

Luminescent iminophosphorane gold, palladium and platinum complexes as potential anticancer agents

2014

A series of coordination gold(III), palladium(II), and platinum(II) complexes with a luminescent iminophosphorane ligand derived from 8-aminoquinoline [Ph3P[double bond, length as m-dash]N–C9H6N] (1) have been synthesized and structurally characterized. The coordination palladium(II) and platinum(II) compounds can evolve further, under appropriate conditions, to give stable cyclometalated endo species [M{κ3-C,N,N-C6H4(PPh2[double bond, length as m-dash]N-8-C9H6N)}Cl] (M = Pd, Pt) by C–H activation of the phenyl group of the PPh3 fragment. Iminophosphorane 1 and the new metallic complexes are luminescent in DMSO or DMSO–H2O (1 : 1 mixture) solutions at RT. The compounds have been evaluated f…

1977

Solutions of chain- (PS-d3) and phenyl ring (PS-d5) deuterated polystyrenes in perdeuterated PS-d8 have been investigated with 1H and 2D NMR relaxation and wide line methods. The intra- and intermolecular parts of the 1H second moments at −100°C are 3,7 G2 and 2,0 G2, respectively, for PS-d3, and 14,7 G2 and ca. 0 G2, respectively, for PS-d5. The intermolecular contribution to the 1H spin lattice relaxation rate, determined at 55 MHz between 150°C and 250°C, is about one third of the total rate in PS-d3, and negligible in PS-d5. We suggest that this contribution is caused by rotational fluctuations of the intermolecular H H vectors. The intramolecular 1H- and 2D-relaxation rates indicate th…

Tetrakis{[(p-dodecacarboranyl)methyl]stilbenyl}ethylene: A Luminescent Tetraphenylethylene (TPE) Core System

2017

The synthesis and spectroscopic characterization of the first set of tetra(p-dodecacarborane-stilbeno)ethylenes (TDSE), substituted either with a methyl or phenyl group in the 2-position (Ccluster) of the ortho-carborane, are described. The complex absorption properties are elucidated by TD-DFT calculations, stressing the importance of through bond conjugation. Enhanced conjugation and restriction of the conformational space are identified as the main factors for boosted luminescence properties in solution compared to tetraphenylethylene (TPE) core, effectively reducing internal conversion (IC). IC is further reduced when aggregate suspensions of our compounds in water are formed, providing…

N-(4-Acetyl-3-methyl-1-phenyl-1H-pyrazol-5-yl)-N-methyl-2-(2-methyl-4-oxo-3,4-dihydroquinazolin-3-yl)benzamide

2013

In the title compound, C29H25N5O3, the dihedral angle between the benzene ring and the pendant quinazoline ring system (r.m.s. deviation = 0.036Å) is 87.60 (17)°. The equivalent angle between the pyrazole ring and the phenyl group is 70.0 (2)°. The dihedral angle between the benzene and pyrazole rings is 30.7 (2)° and overall, the molecular conformation approximates to a Z shape. A short intramolecular C—H...O contact occurs. In the crystal, the molecules are linked by Cπ—H...O-type hydrogen bonds and aromatic π–π stacking interactions [centroid–centroid distance = 3.860 (3) Å], generating a three-…

Über Tetraaryl-methan-analoga in der gruppe 14

1993

The title compounds have been synthesized by Li and Grignard reactions. The crystal structure of Ph3Si-p-Tol has been determined. The substitution of only one phenyl by one p-tolyl group causes only a slight deviation from the ideal S4 symmetry of Ph4Si. Gradual replacement of phenyl by p-tolyl groups leads to increasing low field shifts for all 13C(ipso) atoms. The substitution of the first phenyl group by p-tolyl in Ph4Si and Ph4Sn results in a high field shift both for δ(29Si) (−0.3 ppm) and for δ(119Sn) (−1 ppm). Further replacement shows nearly linear dependencies (Δδ(29Si) = −0.1 ppm, Δδ(119Sn) = + 1.5 ppm per p-tolyl group).

Optically Active Titanium Complexes Containing Linked Amido‐cyclopentadienyl Ligands: Their Use as Asymmetric Hydrogenation Catalysts

1996

Optically active titanium complexes of the formula Ti(η5:η1−C5R4SiMe2NCHMePh)Cl2 (R = H, Me), containing the cyclopentadienyl ligand linked to a chiral 1-phenylethylamido moiety, were synthesized and characterized in both enantiomerically pure forms. A single-crystal X-ray structural analysis of (S)()Ti(η5:η1−C5H4SiMe2NCHMePh)Cl2 shows a conformation in which the phenyl group is turned away from the metal center. NOE measurements suggest that a related structure is retained in solution. Upon activation with n-butyllithium, these complexes show hydrogenation activity toward imines with slight enantioselectivity.

Efficient and Long-Living Light-Emitting Electrochemical Cells

2010

Three new heteroleptic iridium complexes that combine two approaches, one leading to a high stability and the other yielding a high luminescence efficiency, are presented. All complexes contain a phenyl group at the 6-position of the neutral bpy ligand, which holds an additional, increasingly bulky substituent on the 4-position. The phenyl group allows for intramolecular π–π stacking, which renders the complex more stable and yields long-living light-emitting electrochemical cells (LECs). The additional substituent increases the intersite distance between the cations in the film, reducing the quenching of the excitons, and should improve the efficiency of the LECs. Density functional theory…

VEH electronic band structure of poly(phenylsilane)

1993

Abstract The electronic structure of all-trans syndiotactic and isotactic poly(phenylsilane) has been calculated using the valence effective Hamiltonian (VEH) method. The effects of attachment of the phenyl group on the electronic properties of polysilane are analysed in detail. The VEH results show a decrease of ionization potential and an increase of electron affinity which determine an important reduction of the bandgap. These features are correlated with σ−π and σ ∗ −π ∗ interactions between the silicon backbone and the phenyl group.