Search results for "Lone pair"
showing 10 items of 53 documents
In situ study of the phase transition in Bi2Ti4O11
1995
Abstract The paraelectric ⇌ antiferroelectric phase transition of the compound Bi 2 Ti 4 O 11 is studied in situ by electron diffraction and electron microscopy. The transition is reversible and clearly second order. Above T c faint streaking at the superlattice positions persists. In the low-temperature phase, antiphase boundaries with a displacement vector R = 1/2[101] are revealed; they show a finite width, suggesting a gradual displacement of the Bi atoms at the transition. A model for the domain wall configuration is proposed, based on the influence of the lone pairs of Bi 3+ ions at the transition.
Unusual phosphine oxidation: new triazolopyridyl-quinolyl phosphine oxide fluorescent dyes
2015
3-(2-Pyridyl)-[1,2,3]triazolo[1,5-a]quinolylphosphines suffer an unusual phosphine oxidation due to their special geometry that allows a s-donation of the nitrogen (N1) lone pair to phosphorus. This family of compounds behaves as strong fluorophores with high quantum yields.
Formation of optically active oxygen deficient centers in Ge-doped SiO2 by γ- and β-ray irradiation
2010
Abstract We report an experimental study on the comparison between the γ- or β-ray induced Ge related point defects in Ge-doped silica. Silica samples doped with ∼2.2 1017 Ge atoms/cm3 produced with the sol–gel technique have been irradiated with γ-ray or with β-ray. The effects of the irradiation have been investigated by optical absorption, photoluminescence and electron paramagnetic resonance spectroscopy in order to evaluate the generation and the dependence on dose of the Ge(1), E’Ge, GLPC (Germanium lone pair center) and H(II) point defects. No relevant differences between the concentrations of γ- or β-ray induced Ge(1) and E’Ge point defects have been observed and, in addition, it ha…
Concentration growth and thermal stability of gamma-ray induced germanium lone pair center in Ge-doped sol–gel a-SiO2
2009
Abstract We report an experimental study of the concentration growth by γ-ray irradiation of germanium lone pair center (GLPC) in 10 4 part per million molar Ge-doped sol–gel silica. The data show that γ-ray induced GLPC concentration increases linearly up to ∼5 MGy and then it seems to reach a limit value. In addition to the dose dependence, we have studied the thermal stability of the radiation induced GLPC in ambient atmosphere up to 415 °C. We found that the concentration of this latter GLPC starts to decrease at ∼300 °C, at variance to native GLPC, suggesting that the annealing is related to irradiation products. After the thermal treatments the photoluminescence (PL) activity of the γ…
Comparison of &#x03B3; and &#x03B2;-ray irradiation effects in sol-gel Ge-doped SiO<inf>2</inf>
2009
We report an experimental study on the comparison between the γ or β ray induced Ge related point defects in Ge doped silica. Silica samples doped with ∼2.2 1017 Ge atoms/cm3 produced with the sol-gel technique have been irradiated. The effects of the irradiation have been investigated by optical absorption, photoluminescence and electron paramagnetic resonance spectroscopy in order to evaluate the generation and the dependence on dose of the Ge(1), E'Ge, Germanium Lone Pair Center (GLPC) and H(II) point defects. No relevant differences between the concentrations of γ or β ray induced Ge(1) and E'Ge point defects have been observed. In addition, it is found that both irradiations are able t…
Synthesis, characterization and X-ray crystal structures of cyclam derivatives. Part VI. Proton binding studies of a pyridine-strapped 5,12-dioxocycl…
2005
The 14-membered cyclic diamide 1,4,8,11-tetraazacyclotetradecane-5,12-dione (5,12-dioxocyclam) can be considered as a trans-autodiprotected tetraazamacrocycle and provides a convenient starting material for the preparation of macrobicyclic receptors. As an example, the secondary amine nitrogen atoms located at the 1 and 8 positions were cross-bridged with a 1,3-pyridyl strap, affording the constrained ansa-dioxocyclam ligand 1,9,12,18,22-pentaazatricyclo[7.6.6.13,7]docosa-3,5,7(22)-triene-13,19-dione (L1). The proton binding properties of this cage-type compound, which possesses a hemispherical cavity, were fully investigated by spectroscopic (IR, NMR, UV, MALDI-TOF MS), quantum chemical, a…
Ge-doping dependence of gamma-ray induced germanium lone pair centers in Ge-doped silica
2008
We report an experimental study on the y irradiation effects in Ge-doped sol-gel silica samples doped with Ge from 10 2 up to 10 4 part per million molar. The samples were exposed to the radiation generated by a 60 Co source up to an accumulated dose value of 10 MGy. Our data evidence that the γ irradiation significantly increases the number of Germanium Lone Pair Centers (GLPC). Such defects are induced with a concentration that depends on the Ge content of the employed material in those samples where no optical activity related to -s GLPC was detected before irradiation. Furthermore an increase of the GLPC concentration was detected also in a sample that already contains this defect after…
Understanding the selectivity in the formation of δ-lactams vs. β-lactams in the Staudinger reactions of chloro-cyan-ketene with unsaturated imines. …
2014
The reactions of chloro-cyan-ketene with two phenyl substituted unsaturated imines yielding β- or δ-lactams have been investigated using DFT methods at the MPWB1K/6-311G(d,p) level in diethyl ether. The reactions are initialised by the nucleophilic attack of the unsaturated imines on the ketene with formation of zwitterionic intermediates. The subsequent C–C single bond formation at the imine carbon or at the β-conjugated position enables the formation of β- or δ-lactams. Analysis of the energies involved in the two competitive channels explains the selectivity experimentally observed; in the absence of any steric hindrance, formation of δ-lactams is favoured over the formation of β-lactams…
Conformational study of N-alkyl-benzyltetrahydroisoquinolines alkaloid
2003
Abstract An exhaustive conformational study on the benzyltetrahydroisoquinolines (BTHIQ) from ab initio (RHF/6-31G(d)) calculations was carried out. The effects of different substituents at chiral C 1 atom were also considered. Our results indicate that different substituents at C 1 in BTHIQ molecules introduce a significant steric hindrance which, in turn, might be responsible for a conformational restriction favouring or disfavouring the spatial orientation of the lone pairs of N atom allowing or not the electronic attachment with the side chain of Asp residue. These results can serve as an aid for designing suitable structures of BTHIQs for better dopamine D 1 -receptor inhibitory activi…
Ligand engineering in Cu(ii) paddle wheel metal–organic frameworks for enhanced semiconductivity
2020
We report the electronic structure of two metal-organic frameworks (MOFs) with copper paddle wheel nodes connected by a N2(C2H4)3 (DABCO) ligand with accessible nitrogen lone pairs. The coordination is predicted, from first-principles density functional theory, to enable electronic pathways that could facilitate charge carrier mobility. Calculated frontier crystal orbitals indicate extended electronic communication in DMOF-1, but not in MOF-649. This feature is confirmed by bandstructure calculations and effective masses of the valence band egde. We explain the origin of the frontier orbitals of both MOFs based on the energy and symmetry alignment of the underlying building blocks. The effe…