Search results for "Names"
showing 10 items of 6843 documents
A new tetranuclear copper(I) complex based on allyl(5-phenyl-1,3,4-thiadiazol-2-yl)azanide ligand: Synthesis and structural characterization
2015
Abstract By means of alternating current electrochemical technique a new tetranuclear crystalline copper(I) complex [Cu I 4 ( L − ) 4 ] ( L − – allyl(5-phenyl-1,3,4-thiadiazol-2-yl)azanide ion) has been obtained and characterized by X-ray single crystal diffraction ( Sp. gr. I 4 1 / a ) and Raman spectroscopy. The metal center adopts linear arrangement, composed of one thiadiazole N atom from the one L − anion and one azanide N atom of the other L − ligand. A bridged Cu atoms stitch four L − ligands into the firstly observed tetranuclear copper(I) azanide complex with intramolecular Cu(I)⋯Cu(I) interactions at the distance of 2.7451(6) A. Molecular structure and Raman spectrum of the compo…
Breaking Bonds and Forming Nanographene Diradicals with Pressure.
2017
New anthanthrone-based polycyclic scaffolds possessing peripheral crowed quinodimethanes have been prepared. While the compounds adopt a closed-shell butterfly shaped structure in the ground state, a concave-to-convex fluxional dynamic inversion is accessible with a low energy barrier through an open-shell diradicaloid transition-state. Mainly driven by the release of strainattributed to the steric hindrance at the peri position of the anthanthrone core, a low-lying open-shell diradical is accessible through planarization of the core, which can be achieved by thermal excitation in solution. Alternatively, planarization can be achieved by application of mild pressure in the solid state, in w…
Understanding the molecular mechanism of the [3 + 2] cycloaddition reaction of benzonitrile oxide toward electron-richN-vinylpyrrole: a DFT study
2016
The [3 + 2] cycloaddition (32CA) reaction of benzonitrile oxide, BNO 2, with an electron-rich N-vinylpyrrole derivative, NVP 3a, in the presence of dichloromethane, has been theoretically studied using density functional theory (DFT) methods at the B3LYP/6-31G(d) level. This 32CA reaction presents a relatively high activation Gibbs free energy as a result of the low polar character of this zwitterionic-type (zw-type) reaction. Analyses of the calculated relative Gibbs free energies and transition state geometries indicate that the studied 32CA reaction, in excellent agreement with experimental outcomes, takes place in a complete regioselective manner as a consequence of the steric repulsion…
Dinitrogen complexation with main group radicals
2011
In this report we present data from hyperfine sublevel correlation spectroscopy (HYSCORE), an electron paramagnetic resonance (EPR) spectroscopic technique, that reveals weak but distinct interactions between several main group element radicals and physically dissolved dinitrogen in solution. These interactions are the basis for a well-defined coordination of N2 to the paramagnetic centers. The complexes formed are primarily of the van der Waals-type but also feature a non-negligible orbital overlap between dinitrogen and the radicals' SOMO. Our spectroscopic findings are strongly supported by experiments with isotope-labeled 15N2, spectral simulations and quantum chemical and density funct…
Chemistry of density : extension and structural origin of Carnelley's rule in chloroethanes
2012
Low-density liquids and solids, with all intermolecular contacts longer than the sum of van der Waals radii, are formed by all ethanes chlorinated at one locant: CH2ClCH3, CHCl2CH3 and CCl3CH3. The concepts of molecular symmetry described by Carnelley and that of point groups have been compared. Carnelley's rule, when applied to liquid and solid chloroethanes clearly reveals the density dependence on the presence of intermolecular Cl⋯Cl and H⋯Cl short contacts, or their absence due to steric hindrances of overcrowded substituents. At 2.62 GPa, CH2ClCH3 freezes directly into phase II, with molecules arranged into layers with short Cl⋯Cl, H⋯Cl and H⋯H contacts. Only for CH2ClCH3, both the low…
Unveiling the regioselectivity in electrophilic aromatic substitution reactions of deactivated benzenes through molecular electron density theory
2021
The origin of the meta regioselectivity in electrophilic aromatic substitution (EAS) reactions of deactivated benzene derivatives is herein analysed through Molecular Electron Density Theory (MEDT). To this end, the EAS reaction of benzenesulfonic acid with the nitronium NO2+ ion in H2SO4 solution has been studied at the ωB97X-D/6-311G(d,p) level. This reaction takes place through a two-step polar mechanism involving the formation of an unstable cation intermediate. The activation Gibbs free energies associated with the three competitive regioisomeric reaction paths are found in the narrow range of 15.5–18.3 kcal mol−1. By using the Eyring–Polanyi equation a relationship of 18.7 (ortho) : 8…
Energy interactions in amyloid-like fibrils from NNQQNY.
2014
We use large-scale MP2 calculations to analyze the interactions appearing in amyloid fibers, which are difficult to determine experimentally. To this end, dimers and trimers of the hexapeptide NNQQNY from the yeast prion-like protein Sup35 were considered as model systems. We studied the energy interactions present in the three levels of organization in which the formation of amyloid fibrils is structured. The structural changes in the hydrogen bonds were studied too. It was found that the most energetic process is the formation of the β-sheet, which is equally due to both hydrogen bonds and van der Waals interactions. The aromatic rings help stabilize these aggregates through stacking of t…
Cosmic microwave background constraints on secret interactions among sterile neutrinos
2017
Secret contact interactions among eV sterile neutrinos, mediated by a massive gauge boson $X$ (with $M_X \ll M_W$), and characterized by a gauge coupling $g_X$, have been proposed as a mean to reconcile cosmological observations and short-baseline laboratory anomalies. We constrain this scenario using the latest Planck data on Cosmic Microwave Background anisotropies, and measurements of baryon acoustic oscillations (BAO). We consistently include the effect of secret interactions on cosmological perturbations, namely the increased density and pressure fluctuations in the neutrino fluid, and still find a severe tension between the secret interaction framework and cosmology. In fact, taking i…
Revisiting cosmological bounds on sterile neutrinos
2014
We employ state-of-the art cosmological observables including supernova surveys and BAO information to provide constraints on the mass and mixing angle of a non-resonantly produced sterile neutrino species, showing that cosmology can effectively rule out sterile neutrinos which decay between BBN and the present day. The decoupling of an additional heavy neutrino species can modify the time dependence of the Universe's expansion between BBN and recombination and, in extreme cases, lead to an additional matter-dominated period; while this could naively lead to a younger Universe with a larger Hubble parameter, it could later be compensated by the extra radiation expected in the form of neutri…
Hadamard NMR imaging with slice selection
1996
Stochastic NMR imaging is one of the less common NMR imaging techniques. Nevertheless, stochastic rf excitation is characterized by some remarkable features: the rf excitation power is at least two orders of magnitude lower in comparison to conventionally pulsed NMR imaging schemes. Thus, the technique is of interest for imaging of large objects. The systematic noise inherent in images obtained with random noise excitation has been eliminated by using pseudorandom noise together with Hadamard transformation for data evaluation. Data acquisition times are comparable to those of ultrafast imaging techniques. For slice selection, z magnetization is destroyed outside the slice region with speci…