Search results for "transition"
showing 10 items of 3988 documents
Temperature dependence of the static structure factor of ortho-terphenyl in the supercooled liquid regime close to the glass transition
1993
Abstract Studying the temperature dependence of the static structure factor of ortho-terphenyl from the liquid state down to the glass we find that the main peak of S ( Q ) is split into two maxima which behave quite differently. While the maximum at Q =1.4 A −1 is not much affected by the temperature variation the one at 1.9 A −1 is significantly enhanced. This effect is connected with a change of the short range order, i.e. of the intermolecular distances, but evolves continuously. Thus the dynamic anomalies that have been observed in this system around a characteristic temperature T c ≈290 K are not simply due to a discontinuous change in S ( Q ) but can be attributed to the existence of…
Diastereoselectivity in Organometallic Additions to the Carbonyl Group of Protected Erythrulose Derivatives
1998
We have investigated a number of nucleophillic additions to L-erythrulose derivatives (4-12) bearing protective O-silyl, O-benzyl, and O-trityl groups in various relative positions. The results are discussed in the frame of chelated vs nonchelated transition states with additional support of previously published theoretical calculations. Sound evidence appears to exist for the formation of alpha-chelates as the key intermediates in nucleophillic additions to these alpha,beta-dioxygenated ketones. Since such evidence is still lacking in the case of beta-chelates, proposals of their intermediacy have been relegated in favor of the more solid Felkin-Anh model, which predicts the same stereoche…
Surfactant controlled preparation of mesostructured transition-metal oxide compounds
1994
The use of surfactants as templates allows the synthesis of mesostructured transition-metal oxides by a cooperative, interface controlled condensation process.
Electronic Spectra of 2,2‘-Bithiophene and 2,2‘:5‘,2‘ ‘-Terthiophene Radical Cations: A Theoretical Analysis
2001
Analysis of the electronic spectra of 2,2‘-bithiophene and 2,2‘:5‘,2‘ ‘-terthiophene radical cations has been performed by using multiconfigurational second-order perturbation theory (CASPT2). Atomic natural orbital (ANO) type basis sets of split valence quality, including polarization functions on all heavy atoms, have been used. In agreement with experimental data, in the energy range below the lowest optically allowed transition of the respective neutral system, theoretical results predict two main absorption bands for both cations. The 22Au and 32Au states computed at 1.94 and 2.80 eV, respectively, are related to the corresponding band maxima recorded for bithiophene cation. The 12B1 s…
Size-Dependent Spin Switching in Robust Fe-triazole@SiO2 Spin-Crossover Nanoparticles with Ultrathin Shell
2019
<p>A familly of chemically robust hybrid [Fe(Htrz)2(trz)](BF4)@SiO2nanoparticles (NPs) presenting different sizes (from ca. 90 to 28 nm) and an ultrathin silica shell (< 3 nm) have been prepared. All NPs present a characteristic abrupt spin transition with a subsequent decrease in the width of the thermal hysteresis upon reducing the NP size.<br></p>
Steam-activated FeMFI zeolites. Evolution of iron species and activity in direct N2O decomposition
2003
Abstract In this paper the effect of the composition and steaming conditions of FeMFI catalysts on activity in direct N2O decomposition is investigated. MFI zeolites with different framework compositions (FeAlSi, FeGaSi, and FeSi) and without iron ( 100 mbar H2O in N2) favor the extraction of framework iron, enabling the application of lower activation temperatures. The optimum temperature during steam activation is that at which extraction of framework iron is complete without extensive clustering of extra-framework iron species into oxide particles, as was demonstrated by transmission electron microscopy and electrochemical characterization of the samples. Additional experiments show…
Influence of the preparation method on the thiophene HDS activity of silica supported CoMo catalysts
2002
Abstract The effect of the preparation method of CoMo/SiO2 catalysts with and without sodium ions, on the hydrodesulfurization (HDS) of thiophene was investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and N2 physisorption (BET). The samples were prepared by total sol–gel route, by classic wetness impregnation and by co-impregnation, in the presence of nitrilotriacetic acid (NTA), of commercial and sol–gel prepared silica. The influence of sodium ions added to the sol mixture and to the silica before the impregnation with Co and Mo salt solution, was also considered. The presence of sodium favoured the phase transition of amorphous silica to cristobalite with con…
Transition metal ion induced hydrogelation by amino-terpyridine ligands
2014
Hydrogelation behavior of a new class of terpyridine based metallogelators are explored. The gelation and the gel morphology was found to be critically dependent on divalent metal ions, anions and on subtle structural changes on the gelator molecule.
Spin Transition Molecular Materials: New Sensors
2002
This short review article concerns a new family of iron(II) spin transition chain compounds containing 4-R-1,2,4-triazole derivatives whose properties have been followed by several physical techniques. A clear evidence of the LIESST effect at 20 K has been found for one of these materials by 57Fe Mossbauer spectroscopy. Potential applications in terms of pressure and thermal sensors are discussed.
ChemInform Abstract: Diastereoselectivity in Organometallic Additions to the Carbonyl Group of Protected Erythrulose Derivatives.
2010
We have investigated a number of nucleophillic additions to l-erythrulose derivatives (4−12) bearing protective O-silyl, O-benzyl, and O-trityl groups in various relative positions. The results are discussed in the frame of chelated vs nonchelated transition states with additional support of previously published theoretical calculations. Sound evidence appears to exist for the formation of α-chelates as the key intermediates in nucleophillic additions to these α,β-dioxygenated ketones. Since such evidence is still lacking in the case of β-chelates, proposals of their intermediacy have been relegated in favor of the more solid Felkin−Anh model, which predicts the same stereochemical result. …