Search results for "Benzene"
showing 10 items of 1701 documents
Synthesis, Structure, and Reactivity of (Dihydrogen)(hydrido)iron(II) Complexes Bearing Chiral Diphosphanes
2015
The heterolytic cleavage of molecular hydrogen by [Fe(H2O)6][BF4]2 and the chiral phosphane (+)-1,2-bis[(2R,5R)-2,5-dimethylphospholano]benzene [(R,R)-Me-DuPhos] or its enantiomer [(S,S)-Me-DuPhos] yields the (dihydrogen)(hydrido)iron complexes [FeH(2-H2){(R,R)-Me-DuPhos}2]BF4 ([R,R-1]BF4) and [FeH(2-H2){(S,S)-Me-DuPhos}2]BF4 ([S,S-1]BF4), respectively. These complexes are fluxional in solution at room temperature, and the trans isomers are observed at 200 K. The ()-cis-[R,R-1]BF4 complex was identified crystallographically as the only stereoisomer at room temperature. The energetic and structural differences between the cis ( and ) and trans isomers were analyzed from a computational (DFT)…
Prediction of Aquatic Toxicity of Benzene Derivatives to Tetrahymena pyriformis According to OECD Principles
2016
Background: Many QSAR studies have been developed to predict acute toxicity over several biomarkers like Pimephales promelas, Daphnia magna and Tetrahymena pyriformis. Regardless of the progress made in this field there are still some gaps to be resolved such as the prediction of aquatic toxicity over the protozoan T. pyriformis still lack a QSAR study focused in accomplish the OECD principles. Methods: Atom-based quadratic indices are used to obtain quantitative structure-activity relationship (QSAR) models for the prediction of aquatic toxicity. Our models agree with the principles required by the OECD for QSAR models to regulatory purposes. The database employed consists of 392 substitut…
Efficient light-induced phase transitions in halogen-bonded liquid crystals
2016
Here, we present a new family of light-responsive, fluorinated supramolecular liquid crystals (LCs) showing efficient and reversible light-induced LC-to-isotropic phase transitions. Our materials design is based on fluorinated azobenzenes, where the fluorination serves to strengthen the noncovalent interaction with bond-accepting stilbazole molecules, and increase the lifetime of the cis-form of the azobenzene units. The halogen-bonded LCs were characterized by means of X-ray diffraction, hot-stage polarized optical microscopy, and differential scanning calorimetry. Simultaneous analysis of light-induced changes in birefringence, absorption, and optical scattering allowed us to estimate tha…
Structural Signatures of Type IV Isotherm Steps: Sorption of Trichloroethene, Tetrachloroethene, and Benzene in Silicalite-I
2002
We have investigated by in situ neutron diffraction the structural properties of C2HCl3, C2Cl4, and C6D6 sorbed phases in silicalite-1. Our motivation is to correlate the structure of these three confined species to the fact that their adsorption isotherms are characterized by no step, one step, and two steps, respectively. From our detailed neutron diffraction investigation, we deduce that the adsorption isotherm steps are not signatures of phase transitions but are correlated to the different adsorption stages observed during the silicalite-1 loading. For C6D6, such a loading is a three stage process (the C6D6 molecules fill successively, the intersections, then the straight channels and …
Optical suppression of ferroelectricity in polysiloxane copolymers with chiral and photochromic side groups
1998
The ferroelectricity of surface-stabilized aligned films of polysiloxane copolymers containing chiral esters and photochromic azobenzene moieties within the side groups is suppressed on UV irradiation and is rebuilt on visible irradiation. The liquid crystalline polymer (Sc* 64 SA 80 i) shows ferroelectric behavior below 64°C. The photoinduced modification of supramolecular order and the corresponding changes in its dynamics are studied by polarized UV/vis spectroscopy and broad band dielectric spectroscopy (10−2–105 Hz). The dielectric measurements show that UV irradiation causes a loss of ferroelectricity within an interval of 10 K below the phase transition temperature. The photochemical…
A theoretical study of the lowest electronic states of azobenzene: the role of torsion coordinate in the cis-trans photoisomerization
2003
In the present paper we report the results of a multiconigurational computational study on potential- energy curves of azobenzene along the NN twisting to clarify the role of this coordinate in the decay of the S2(pp*) and S1(np*) states. We have found that there is a singlet state, S3 at the trans geometry, on the basis of the doubly excited coniguration n 2 p* 2 , that has a deep minimum at about 90 of twisting, where it is the lowest excited singlet state. The existence of this state provides an explanation for the short lifetime of S2(pp*) and for the wavelength-dependence of azobenzene photochem- istry. We have characterized the S1(np*) state by calcu- lating its vibrational frequencie…
Photochemical formation of [4.4.4](1,3,5)cyclophanes from 1,3,5-tris(3-phenylpropenoyl)benzenes
2004
Abstract Irradiation of 1,3,5-tris(3-phenylpropenoyl)benzene ( 1a ) yields in solution a dimer 2a by a threefold head-to-head/anti [2π+2π]cycloaddition. The stereochemistry of this [4.4.4](1,3,5)cyclophane was determined by 1H and 13C NMR studies including NOE measurements and a calculation of the AA′MM′ spin pattern of the methine protons. In contrast to the solution photochemistry, which is presumably controlled by the arrangement of an excimer, the irradiation in the crystalline state leads by a topochemical control to a dimer 3a , which contains a single four-membered ring.
Highlights of metal ion-based photochemical switches
2014
Abstract Selected metal complexes behaving as photochemical switches, mostly operating by light emission/absorption without the intervention of any added chemical species, are reviewed. First, the switching mechanisms are analyzed to offer readers an easier understanding of the described systems. Examples of photochemical switching based on complexation/decomplexation processes and photo-bistable systems, comprising metal complexes with azobenzene, azopyridine, diarylethene, spirocyclic and rhodamine ligands, make the central body of the review. These examples were chosen to provide an overview of the evolution of metal-ion based photochemical switches, collecting together historical cases …
Photochemical behavior in azobenzene having acidic groups. Preparation of magnetic photoresponsive gels
2011
[EN] The photochemistry of three azobenzenes representing contrasting photochemical behaviors is described in the present work. Thus, Methyl Orange (MO, 4-[[(4-dimethylamino)phenyl]-azo]benzenesulfonic acid sodium salt, hereinafter (1) and 4-hydroxyazobenzene-4'-sulfonic acid (2) undergo in water fast photochemical proton shift, with decays in the microsecond timescale. In contrast to the previous cases, azobenzene-4,4'-dicarboxylic acid (3) undergoes photoisomerization in water. This photochemical behavior allows the preparation of aqueous gels with Aerosil as gelating agent (5% weight) exhibiting high cyclability and photoreversible isomerization of the trans to cis (300 nm irradiation) a…
Similar chemical structures, dissimilar triplet quantum yields: a CASPT2 model rationalizing the trend of triplet quantum yields in nitroaromatic sys…
2019
The photophysics of nitroaromatics compounds stand out for being characterized by an ultrafast decay into the triplet manifold and by a significant value of the triplet quantum yield. The latter quantity can change dramatically from one system to another, as proven for the molecules 2- nitronaphthalene, 1-nitronaphthalene, and 2methyl-1nitronaphthale, whose triplet quantum yield have been previously measured to be 0.93 ± 0.15, 0.64 ± 0.12, and 0.33 ± 0.05, respectively (J. Phys. Chem. A 2013, 117, 14100). In the present contribution we rationalize the reported trend for the triplet quantum yield on the basis of the different ability that the excited S 1 state has in the three molecules to r…