Search results for "Intramolecular force"
showing 10 items of 599 documents
Orientation dependence of high-order harmonic generation in molecules
2003
We present two- and three-dimensional model calculations of high-order harmonic generation in ${\mathrm{H}}_{2}^{+}.$ The harmonic spectra exhibit clear signatures of intramolecular interference. An interference minimum appears at a harmonic order that depends on the molecular orientation. Harmonic generation in three-center molecules is studied on the basis of two-dimensional calculations for a ${\mathrm{H}}_{3}^{2+}$ model system. From analytical considerations, the orientation dependence of the harmonic intensities in three-center molecules exhibits a double minimum due to intramolecular interference. In the numerical results, the double minimum is broadened into a single wide minimum. T…
Complex chemistry with complex compounds
2016
In recent years gas-phase chemical studies assisted by physical pre-separation allowed for the investigation of fragile single molecular species by gas-phase chromatography. The latest success with the heaviest group 6 transactinide seaborgium is highlighted. The formation of a very volatile hexacarbonyl compound Sg(CO)6 was observed similarly to its lighter homologues molybdenum and tungsten. The interactions of these gaseous carbonyl complex compounds with quartz surfaces were investigated by thermochromatography. Second-generation experiments are under way to investigate the intramolecular bond between the central metal atom of the complexes and the ligands addressing the influence of re…
Electrochemical study of intramolecular charge transfer complexes derived from 1,4-naphthoquinone Part 1. Electroreduction
1995
Abstract Electrochemical investigations (polarography, cyclic voltammetry, rotating ring-disk electrode voltammetry) of intramolecular charge transfer complexes (AC) derived from 1,4-naphthoquinone were performed in acetonitrile. It is concluded that in the first one-electron stage of its electrochemical reduction the AC is in a complexed form. At the same time the amino moiety, which shows a marked inductive (−I) effect, acts as an electron donor in the donor-acceptor (D-A) interaction. Facilitation of the reduction of the quinone part by the aryl amine residue is compensated by the D-A interaction, which makes the electroreduction more difficult. By using ultramicroelectrodes it was shown…
The Influence of Intramolecular Coordination and Ring Strain on the Polymerization Potential of Cyclic Stannasiloxanes
2008
ChemInform Abstract: Synthesis of 1,2-Disubstituted Indoles from α-Aminonitriles and 2-Halobenzyl Halides.
2016
The α-alkylation of deprotonated Strecker products derived from primary amines and aromatic aldehydes with 2-halobenzyl halides furnishes intermediates that can be cyclized to 1,2-disubstituted indoles in moderate to high yields (up to 94% over two steps) by microwave-assisted copper- or palladium-catalyzed intramolecular cross-coupling.
Small-angle X-ray scattering reveals differences between the quaternary structures of oxygenated and deoxygenated tarantula hemocyanin
1996
Small-angle X-ray scattering (SAXS) curves have been recorded for the oxygenated and deoxygenated states of the 4 x 6-meric hemocyanin from the tarantula Eurypelma californicum. A comparison of the curves shows that the quaternary structures of the two states are different by three criteria, which all indicate that the hemocyanin is less compact in the oxygenated compared to the deoxygenated form: (a) The radius of gyration is 8.65 +/- 0.05 nm for the deoxy- and 8.80 +/- 0.05 nm for the oxy-form. (b) The maximum particle dimension amounts to 25.0 +/- 0.5 nm for the deoxy- and to 27.0 +/- 0.5 nm for the oxy-form. (c) A dip in the intramolecular distance distribution function p(r) is more pro…
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…
(o-Hydroxyphenyl)methylphosphonic Acids: Spectrophotometric determination of their pKavalues and of the deprotonation sequence
1993
UV/VIS Absorption spectra of nitrosubsituted (o-hydroxyphenyl)methylphosphonic acids (o-(phosphonomethyl)phenols) were measured as a function of pH at 25° in 0.1M NaClo4 solutions. Computational treatment of the whole set of optical density data between 200 and 500 nm resulted in the determination of the dissociation constants of these polyacids and also of the individual electronic spectra of all the species involved in the deprotonation sequence. The spectral behavior gives information on the structure of the anions formed and consequently the order of the subsequent deprotonation steps could be deduced. For the (2-hydroxy-3-nitro(or 5-nitro)phenyl)methylphosphonic acid and the 2-hydroxy-…
Site selectivity in excited-state intramolecular proton transfer in flavonols
2001
Abstract To investigate 4′-(diethylamino) (FET) and 4′-N-(15-azacrown-5) (FCR) derivatives of 3-hydroxyflavone in binary solvents and erythrocyte ghosts, we used the red-edge excitation spectroscopy (REES). The results obtained prove the existence of spectral heterogeneity of flavonols in the studied systems. The effect manifests itself in the dependence of the efficiency of excited-state intramolecular proton transfer (ESIPT) on the excitation frequency. The electro-optical absorption method (EOAM) was used to measure the dipole moments of the normal form of FET. The electric dipole moments in the ground (μg) and excited Franck–Condon ( μ e FC ) states have the values 22.7×10−30 and 53.3×1…
Intramolecular Communication in Anionic Oxidized Phosphanes through a Chelated Proton
2015
Oxidation of the 1,2-(PR2 )2 -1,2-closo-C2 B10 H10 (R=Ph, iPr) platform with hydrogen peroxide in acetone is a two-step procedure in which partial deboronation of the closo cluster and oxidation of the phosphorus atoms occur. Based on NMR spectroscopic and kinetic data, we demonstrate that the phosphorus atoms are oxidized in the first step, followed by cluster deboronation. DFT calculations and natural-bond orbital (NBO) analysis were used to obtain insight into the electronic structures of diphosphane ortho-carborane derivatives.