Search results for "Paramagnetic"

Isolation of the CH3˙ rotor in a thermally stable inert matrix: first characterization of the gradual transition from classical to quantum behaviour …

2014

International audience; Matrix isolation is a method which plays a key role in isolating and characterizing highly reactive molecularradicals. However, the isolation matrices, usually composed of noble gases or small diamagnetic molecules,are stable only at very low temperatures, as they begin to desegregate even above a few tens of Kelvin.Here we report on the successful isolation of CH3 radicals in the cages of a nearly inert clathrate–SiO2matrix. This host is found to exhibit a comparable inertness with respect to that of most conventionalnoble gas matrices but it is characterized by a peculiar thermal stability. The latter property is related to thecovalent nature of the host material a…

Properties of HO2• radicals induced by γ-ray irradiation in silica nanoparticles

2014

Abstract We report an experimental investigation on the effects of γ -ray irradiation in several types of silica nanoparticles previously loaded with O 2 molecules. They differ in specific surface and average diameter. By electron paramagnetic resonance (EPR) measurements we observe the generation of about 10 18 HO 2 • /cm 3 interstitial radicals. These radicals are induced by reaction of interstitial O 2 molecules with radiolytic H atoms, as previously suggested for O 2 -loaded bulk a-SiO 2 samples. However, at variance with respect to bulk materials, our experimental evidences suggest a different generation process of HO 2 • radical. In fact, by a detailed study of samples exposed to D 2 …

Intrinsic defects induced by β-irradiation in silica

2002

We report an electron paramagnetic resonance study of defects induced by β-irradiation in natural and synthetic samples of high purity commercial silica. Data are collected for the E′ centers and a resonance satellite signal split by 1.36 mT. By comparison with the effects of γ-irradiation it is shown that the mechanisms of defect generation are the same for the two irradiation sources and that in the high-dose limit they involve intrinsic defects of the glassy matrix. Moreover, the high concentration of defects generated by β-irradiation modifies the EPR spectrum due to spin–spin interaction.

Exchange interactions through hydrogen-bond bridges. Crystal structure, spectroscopic characterisation and magnetic properties of the complex [{Cu(en…

1998

Abstract The structure and spectroscopic and magnetic properties of [{Cu(en)}2(μ-egta)]·4H2O (H4egta = 3,12-bis(carboxymethyl)-6–9-dio 3,12-diazatetradecanedioic acid) are described. The compound is built of centrosymmetric neutral dimeric {[Cu(en)}2(μ-egta)] entities linked through hydrogen bonds involving water molecules. -NH2 groups and -CO2 groups, affording a three-dimensional framework. The egta anion displays an opened-up structure acting as a bridging ligand between two copper atoms. The coordination geometry about the metal atoms can be viewed as 4 + 1 + 1 (CuN3OO′O″ chromophores). The EPR spectra are indicative of an essentially dv−v ground state for the copper(II) ions. Magnetic …

Investigation on the ganaration process of HO2• radicals by γ-ray irradiation in O2-loaded fumed silica

2013

Abstract We report an experimental investigation on the effects of γ-ray irradiation in three types of fumed silica previously loaded with O 2 molecules. Our data indicate that the main effect of irradiation in these systems is to generate a very large concentration of HO 2 interstitial radicals (about 10 18  molecules/cm 3 ). Furthermore, the number of generated HO 2 was found to be larger in the samples with higher O 2 contents before irradiation. This correlation suggests that HO 2 radicals are induced by reaction of interstitial O 2 molecules with radiolytic H atoms, as previously suggested for O 2 -loaded bulk amorphous silicon dioxide (a-SiO 2 or silica) samples. However, at variance …

Preparation and structure of the 17-electron (η5-C5R5)Mo(OH)2(dppe) (R=Me, Et) organometallic compounds containing two gem-terminal hydroxide ligands

2000

International audience; Oxidation of (η5-C5R5)MoH3(dppe) (R=Me, Et) by Cp2Fe+ in wet THF leads to the formation of the corresponding (η5-C5R5)Mo(OH)2(dppe). These compounds show a low-potential reversible oxidation wave. The structure of the C5Et5 complex has been confirmed by X-ray diffraction methods: triclinic; space group ; a=11.030(1); b=12.533(1); c=16.241 (1) Å; α=68.585(7); β=75.197(5); γ=83.991(7)°; V=2020.6(3) Å3; Z=2; Dcalc=1.324 g cm−3, μ(Mo–Kα)=0.441 mm−1; R1=0.0325; wR2=0.0875 for 415 parameters and 6823 independent reflections [Rint=0.0177] with I=2σ(I). The molecule shows a four-legged piano-stool geometry with two terminal OH ligands in a relative trans configuration. The c…

Influence of hydrogen on paramagnetic defects induced by UV laser exposure in natural silica

2005

Diffusion limited reactions of point defects were investigated in amorphous SiO2 exposed to UV laser light. Electron spin resonance and in situ absorption measurements at room temperature evidenced the annealing of E' centers and the growth of H(II) centers both occurring in the post-irradiation stage and lasting a few hours. These transients are caused by reactions involving molecular hydrogen H2, made available by dimerization of radiolytic H0.

Strong Ferromagnetic Coupling in Linear Mixed μ-Acetato, μ-Hydroxo Trinuclear Copper(II) Complexes withN-sulfonamide derivatives − Synthesis, Structu…

2002

New CpCrCl2(PR3) complexes: physical properties and reduction chemistry

1998

Abstract Compounds CpCrCl2L ( L = PMe 2 Ph , 1 , PMePh 2 , 2 ; PPh 3 , 3 ) have been prepared. Their magnetic moment is in accord with the presence of three unpaired electron and a variable temperature 1H NMR investigation of 1 shows Curie-Weiss behavior. The 1H NMR, EPR and UV-visible spectra are in agreement with those of other previously reported compounds of the same family. An electrochemical investigation shows the accessibility of an irreversible reduction process. A parallel sodium reduction investigation of complexes CpCrCl2L (L = PMe3 and η1-dppe) suggests tjat the reduction process is followed by immediate chloride loss, and then by a ligand redistribution process to afford chrom…

A two-dimensional radical salt based upon BEDT-TTF and the dimeric, magnetic anion [Fe(tdas)2]22−: (BEDT-TTF)2[Fe(tdas)2] (tdas = 1,2,5-thiadiazole-3…

2002

In an attempt to synthesize new synthetic metals which couple magnetic properties to conductivity, we prepared the novel salt (BEDT-TTF)2[Fe(tdas)2] [BEDT-TTF = bis(ethylenedithio)tetrathiafulvalene, hereafter referred to as ET; tdas = 1,2,5-thiadiazole-3,4-dithiolate] by the electrocrystallization technique. The crystal structure of this compound, as determined by single crystal X-ray diffraction, contains conducting, organic ET layers separated by dimerized, magnetic [Fe(tdas)2]22− anions. Due to the magnetic insulating ground electronic state of the ET layer, thermally activated conductivity is observed, with a room temperature value of about 1 S cm−1. This salt was also characterized by…