Search results for "PHOTOCHEMISTRY"
showing 10 items of 2034 documents
New Carbaalanes − (AlMe)8(CCH2Me)5(C≡C−Me) and the THF Adduct (AlMe)8(CCH2Me)5H·2THF
2001
The hydroalumination of Me2Al−C≡C−Me with a large excess of Me2AlH afforded the arachno-carbaalane (AlMe)8(CCH2Me)5H (4) by the release of AlMe3. 4 is almost insoluble in noncoordinating solvents and could not be purified by recrystallization. On an attempt to recrystallize 4 from a THF solution, the adduct (AlMe)8(CCH2Me)5H·2THF (5) was isolated as the first stable ether adduct of a carbaalane. Crystal structure determination revealed a cube of eight aluminium atoms, five faces of which are bridged by C−CH2Me groups. The sixth face is µ2-bridged by a hydrogen atom, and two opposite aluminium atoms of this face are coordinated by one THF ligand each. When the excess of dimethylaluminium hyd…
Structural Versatility of Anion−π Interactions in Halide Salts with Pentafluorophenyl Substituted Cations
2008
A series of pentafluorophenyl substituted ammonium, iminium, amidinium, and phosphonium halides are presented which show extensive anion-pi interactions. Hereby, the well-known anion-donor-pi-acceptor as well as "eta6" anion-pi-complex type interactions are observed. The latter is supported by fixation of the anion on top of the aromatic system through hydrogen bonding. This arrangement was investigated by theoretical methods showing a highly attractive anion-pi interaction. In addition an eta2-type coordination of the anions to only two C-atoms of the electron-deficient ring system is described.
Proton-Coupled Electron Transfer in Ferrocenium–Phenolate Radicals
2013
Electron and proton transfer (ET, PT) can be intimately coupled, provided suitable redox and acid/base sites are available. The amide-linked ferrocene–phenol H-1 is deprotonated to the phenolate [1]– by phosphazene bases and oxidized to the ferrocenium ion [H-1]+ by silver hexafluoroantimonate. Concomitant oxidation and deprotonation yields the radical [1]•, featuring a characteristic near-IR absorption band. The ground state of [1]• is best described as the ferrocenium–phenolate zwitterion [1b]• with a dynamic dissymmetric N···H···O hydrogen bond (PT). The ferrocenium–iminolate N···H–O tautomer [1b]•-NHO′ can undergo a thermal structural rearrangement to the high-energy OH···O tautomer [1b…
Effects induced by 4.7 eV UV laser irradiation on pure silica core multimode optical fibers investigated by in situ optical absorption measurements
2011
We investigated by in situ optical absorption measurements the effects induced by 4.7 eV UV laser irradiation on pure silica core optical fibers. Laser irradiation with 100 MWcm−2 laser intensity generates in the fiber E′ centers which partially decay after irradiation due to their reaction with diffusing H2. An absorption band peaked at 5.3 eV is observed to grow in the post-irradiation stage with a kinetics anti-correlated to the decay of the 5.8 eV band of the E′ centers. The defect absorbing at 5.3 eV is proposed to be formed by trapping on pre-existing precursors of hydrogen atoms made available by breaking of H2 on E′.We also show by repeated irradiation experiments that the 5.3 eV-ab…
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 …
Photochemical Size Reduction of CdSe and CdSe/ZnS Semiconductor Nanoparticles Assisted by nπ* Aromatic Ketones
2009
A novel effect of n pi* aromatic ketones on the quantum dots optical properties is reported. By controlling experimental conditions such as time of irradiation, presence of air in the media, hydrogen donor capacity of the solvent, and irradiation wavelength, core and core-shell CdSe QDs can be resized as convenient.
Au/TiO2-CeO2 Catalysts for Photocatalytic Water Splitting and VOCs Oxidation Reactions
2016
Photocatalytic water splitting for H2 production and photocatalytic oxidation of 2-propanol, an example of volatile organic compounds, were investigated over TiO2 catalysts loaded with gold and/or ceria. In the water splitting reaction the presence of gold only slightly affected the performance of TiO2 whereas the presence of CeO2 had a more remarkable positive effect. In the 2-propanol oxidation Au/TiO2 was the most active sample in terms of alcohol conversion whereas Au/TiO2-CeO2 exhibited the highest CO2 yield. On the basis of characterization experiments (X-Ray Diffraction (XRD), Energy Dispersive X-ray Analysis EDX, surface area measurements, Diffuse Reflectance Spectroscopy (DRS) and …
ESI-FTICR investigation of triethylammonium ion-driven resorcin[4]arene dimer formation and structure
2002
In the course of mass spectrometric measurements a self-assembled hydrogen bonded resorcinarene dimer was observed, the formation of which was driven by the binding of triethylammonium ion as a guest and as an ionic label.
Boron Nitride‐supported Sub‐nanometer Pd6 Clusters for Formic Acid Decomposition: A DFT Study
2017
A periodic, self-consistent planewave DFT study was carried out to explore the potential use of Pd6 clusters supported on a boron nitride sheet as a catalyst for the selective decomposi- tion of formic acid (HCOOH) to CO2 and H2. The competition between formate (HCOO) and carboxyl (COOH) paths on cata- lytic sites, with different proximities to the support, was stud- ied. Based on energetics alone, the reaction may mainly follow the HCOO route. Slightly lower activation energies were found at the lateral sites of the cluster as compared to top face sites. This is particularly true for the bidentate to monodentate HCOO conversion. Through comparison of results with similar studies on HCOOH d…
Hydrogen bonded calixarene capsules kinetically stable in DMSO.
2002
Half-life times up to 4 days in DMSO at room temperature are observed for the decomposition of dimeric capsules of urea substituted calix[4]arenes held together by a combination of hydrogen bonds, mechanical entanglement and cation–π interactions.