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Mutual Orientation (mutual + orientation)
Selected AbstractsRaman and Rayleigh scattering study of crystalline polyoxyethyleneglycolsCRYSTAL RESEARCH AND TECHNOLOGY, Issue 4-5 2005M. Kozielski Abstract Results of the study of Raman and Rayleigh scattering in crystalline polyoxyethyleneglycols (PEG) and PEG 1500 aqueous solution are reported. The conformational changes of the polymer chain have been studied as a function of PEG water solution concentration and molecular weight. Intensity ratios of the gauche and trans conformation around C,C and C,O bonds have been estimated from the Raman spectra. Moreover, from the Raman band parameters the values of the order parameters versus aqueous solution concentration have been determined. The influence of an external electric field on these parameters has been analysed. Mutual orientation of polyoxyethyleneglycol chains in the crystalline and liquid state has been studied on the basis of the angular correlation parameters obtained from the Rayleigh band intensity as a function of aqueous solution concentration and molecular weight. (© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Structural transformations in organic crystals during photochemical reactionsJOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 10 2004Ilona Turowska-Tyrk Abstract In the 1980s and 1990s, x-ray studies of the photochemical reaction course in crystals dealt with the analysis of changes in cell constants or movements of atom groups inside molecules. This review presents the results of crystallographic studies on the monitoring of the behaviour of whole molecules in organic crystals during photochemical reactions. Papers on this subject started to appear only a few years ago. The studies showed quantitatively that reactant and product molecules do not take a fixed position in a crystal during the reaction. The product molecules move smoothly to a position assumed in the pure product crystal and the reactant molecules move from a position occupied in the pure reactant crystal. Moreover, with the reaction progress the adjacent reactant molecules gradually come closer and change their mutual orientation to resemble the product. The analysis of the photoreaction kinetics in crystals is also presented. Copyright © 2004 John Wiley & Sons, Ltd. [source] Structural study of ethyl 3-arylcarbamoyl-2,3-diazabicyclo[2.2.1]hept-5-ene-2-carboxylates: conformation and transmission of substituent effects across the diazabicycloheptene ring,JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 11 2001A. Perjéssy Abstract Nine new ethyl 3-arylcarbamoyl-2,3-diazabicyclo[2.2.1]hept-5-ene-2-carboxylates were prepared by a [4,+,2] cycloaddition and their FTIR, 1H, 13C and 15N NMR spectra were measured and assigned. Single crystals were grown for five compounds and their X-ray data were obtained. The electronic structure and the conformations were calculated by the semi-empirical AM1 method. Using correlations between the spectral, empirical and theoretical structural data, the transmission of substituent effects and the preferential conformation connected with the consecutive double nitrogen inversion and regarding the mutual orientation of NH and CO bonds were investigated. The results are compared with those for a previously reported series of analogous ethyl 2-arylcarbamoyl-4,5-dimethyl-1,2,3,6-tetrahydropyridazine-1-carboxylates. Copyright © 2001 John Wiley & Sons, Ltd. [source] The effects of degeneracy of atomic levels on single-photon emission via Raman scatteringLASER PHYSICS LETTERS, Issue 8 2008V.A. Reshetov Abstract The three-level , -type atom with degenerate atomic levels is considered, one of its transitions being driven by the coherent field, the other being coupled to the single-mode quantized field of the high-Q cavity. The probability of emission of a single photon in the cavity via Raman scattering versus the mutual orientation of polarization vectors of the cavity mode and of the driving coherent pulse is studied. The efficiency of the retrieval of a single-photon excitation, stored in the atomic ground state (as suggested, e.g., in paper [1]), versus the mutual orientation of polarizations of cavity modes and of the coherent "write" and "read" pulses is also investigated. The numerical calculations are carried out for the transitions between hyperfine components of the ground 6S1/2 and excited 6P3/2 states of Cesium atoms, which were exploited in the experiments [1]. The optimal polarizations providing the maximum probability of photon emission and maximum retrieval efficiency are determined. (© 2008 by Astro Ltd., Published exclusively by WILEY-VCH Verlag GmbH & Co. KGaA) [source] Interplay between dipolar, stacking and hydrogen-bond interactions in the crystal structures of unsymmetrically substituted esters, amides and nitriles of (R,R)- O,O,-dibenzoyltartaric acidACTA CRYSTALLOGRAPHICA SECTION B, Issue 3 2001Urszula Rychlewska The compounds analysed are the O,O,-dibenzoyl derivatives of (R,R)-tartaric acid, asymmetrically substituted by ester, amide and nitrile groups. Benzoylation does not introduce drastic changes to the molecular conformation. All investigated molecules adopt the planar T conformation of the four-carbon chain with noticeably smaller departures from the ideal conformation than observed in the nonbenzoylated analogs. Primary and secondary amides always orient the C=O bond antiperiplanar (a) with respect to the nearest C*,O bond, while methylester groups adjust their conformation to that adopted by the amide substituent situated at the other end of the molecule. Tertiary amides and carboxyl groups place their carbonyls at the same side as the nearest C*,O bond (the s form), but often deviations from coplanarity of the two bonds are significant and higher than those observed in the nonbenzoylated series. The results presented demonstrate the importance of dipole/dipole interactions between CO and ,C*H groups in stabilizing the molecular conformation, and between carbonyl groups in stabilizing crystal packing of the molecules that lack classical hydrogen-bond donor groups. An illustration is provided as to how a small change in mutual orientation of molecules arranged in a close-packed fashion causes a change in the character of intermolecular interactions from van der Waals to sandwich stacking between the benzoyloxy phenyls, and to dipolar between the benzoyloxy carbonyls. Hydrogen-bonded molecules tend to orient in a head-to-tail mode; the head-to-head arrangement being limited to cases in which terminal carbonyl groups are situated at one side of the molecule. The orientation of the benzoyloxy substituents with respect to the carbon main chain is such that the (O=)C,O,C,H bond system often deviates significantly from planarity. [source] Pyrazole-Bridged NHC Ligands and Their Dimetallic (Allyl)palladium ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 3 2008Ulrich J. Scheele Abstract A set of compartmental pyrazole-based ligands with appended NHC donors has been synthesized and isolated as [H4L]Cl3 and [H3L](PF6)2 salts. Dinuclear (allyl)palladium complexes of these ligands are conveniently accessible via the in situ prepared silver species. Three complexes [(allyl)2Pd2L]PF6 and one derivative [(methallyl)2Pd2L]PF6 have been characterized crystallographically, which revealed that the metal ions are positioned in close proximity [d(Pd···Pd) = 3.97,4.05 Å], with two possible mutual orientations of the (meth)allyl ligands within the dimetallic pocket. NMR spectroscopy shows slow interconversion of these isomers (k = 0.05,0.4 s,1), where the (meth)allyl ligands are detached trans to the carbene during this ,3 -,1 -,3 dynamic process.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] | |||||||||||||