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151.
J. Baran A. J. Barnes M. K. Marchewka A. Pietraszko H. Ratajczak 《Journal of Molecular Structure》1997,416(1-3):33-42
The crystal structure of bis(betaine)-selenic acid has been determined by X-ray diffraction as orthorhombic, space group Pbca, with a = 11.591(2), b = 22.930(5), c = 12.045(2) Å and Z = 8. The crystal comprises hydrogen selenate ions, HSeO−4, and two distinct betaine molecules, which are held together into a complex by short hydrogen bonds. One of the betaine molecules is present as the zwitterion form (CH3)3N+---CH2---COO− and the second occurs as the protonated form (CH3)3N+---CH2---COOH. Powder FTIR and Raman spectra were measured. An assignment of the observed bands to vibrations of the hydrogen bonds and internal vibrations of the hydrogen selenate ion and the betaine molecules is proposed. 相似文献
152.
Svetlana V. Amosova Vladimir A. Shagun Natalia A. Makhaeva Konstantin A. Lysenko 《Journal of organometallic chemistry》2007,692(16):3307-3315
The structure of 2,4-dibromo-2-dibromomethyl-3,3-dimethyl-1-selena-3-silacyclopentene-4, formed by regioselective electrophilic addition of SeBr4 to dimethyl diethynyl silane, has been determined using X-ray analysis technique. Quantum chemistry methods were used to study elementary stages of the reaction. It was found that the first stage consisted of SeBr4 conversion into bimolecular complex Br2?SeBr2, initiated by dimethyl diethynyl silane. Possible formation of five-membered and six-membered heterocycles involves different cyclization mechanisms. The formation of only five-membered heterocycle is explained by kinetically preferable ring closure through four-center transition state. The conclusions obtained by calculations were confirmed by monitoring of the reaction using 1H NMR method. 相似文献
153.
K. Dimroth A. Berndt F. Br A. Schweig R. Volland 《Angewandte Chemie (International ed. in English)》1967,6(1):34-40
The distribution of the unpaired electron over the oxygen and the 24 carbon atoms in the free 2,4,6-triphenylphenoxy radical was determined by electron spin resonance spectroscopy and quantum-mechanical approximation methods. The hyperfine splitting was evaluated with the aid of the spectra of triphenylphenoxyls deuterated in some or all of the substituent phenyl groups. The results of the quantum-mechanical approximations were checked by recording the ESR spectra of triphenylphenoxyls labeled with 13C in positions 1,2,3, or 4 of the central ring. The spin density distribution permits a first discussion of the 17O-coupling constants of correspondingly labeled triphenylphenoxyl and other organic free radicals. 相似文献
154.
The dipole dynamics and α-relaxation behaviour of polyvinyl chloride PVC, poly(ethylene-co-vinyl-acetate) EVA70 and blend of them EVA70/PVC have been investigated by differential scanning calorimetry (DSC) and dielectric relaxation spectroscopy (DRS). The differential scanning calorimetry (DSC) thermograms measured on samples show a single glass transition in the analysed temperature range. These three polymers are wholly amorphous and pure PVC and pure EVA70 are miscible in the ratio 1:1. The glass transition temperature Tg decreases significantly with presence of EVA70. Furthermore, the values of apparent activation energies for molecular motions at the α-relaxation and the values of fragility index have also been determined for each sample using Moynihan expression for DSC results and Vogel-Fulcher-Tammann-Hesse (VFTH) form for DRS results. It is shown a large dependence of all the values of these parameters with the content of EVA70. Comparing these three polymers, we found that the more fragile glass forming liquid is the PVC. Fragility decreases drastically with EVA70 content. EVA70 and EVA70/PVC blend exhibit practically the same behaviour. The effect of inter- and intra-molecular interactions on fragility is discussed to explain these variations. 相似文献
155.
Analysis of changes in 35Cl NQR frequency of complexes MCl4.L and MCl4.2L for M = Si, Ge, Sn and Ti was performed. The population of the atomic orbitals was calculated by the quantum chemistry methods PM3 and INDO. The results provided an explanation of the changes in 35Cl NQR frequency and the asymmetry parameter upon complex formation. In the complexes of non-transition elements, a decrease in 35Cl NQR frequency is first of all related to increasing population of pz orbitals on Cl atoms. In the complexes of Ti, the increase in 35Cl NQR frequency depends on a decrease in the pπ to dπ electron density transfer. 相似文献
156.
157.
Several new methyl-substituted indenyl ferrocenes were prepared by metathesis reactions of the indenide (generated from the appropriate indene with BuLi) with ferrous chloride. The indenides used to prepare new ferrocenes were: 2-methyl-, 1,2-dimethyl-, 4,7-dimethyl-, 1,4,7-trimethyl-, and 1,3,4,7-tetramethyl-indenide. These indenyl ferrocenes, along with those prepared from indenide, 1-methylindenide, and 1,3-dimethylindenide, were then characterized by 1H and 13C NMR, UV/visible spectroscopy, cyclic voltammetry and mass spectrometry. The cyclic voltammetry showed an additive relationship between oxidation potential and the number of methyl groups which is also position-dependent, whereas the UV/visible spectra showed two absorptions essentially unaffected by methyl substitution. Additionally, bis(2-methylindenyl)iron(II) and bis(4,7-dimethylindenyl)iron(II) were characterized by X-ray crystallography. 相似文献
158.
159.
160.
This review addresses the special problems associated with the micro-structural characterization of thin and ultrathin organic films, primarily by optical spectroscopies. Films which are deposited by Langmuir-Blodgett techniques, self-assembly chemistry, and bulk film deposition techniques are considered. The use of enhanced optical excitation using surface phasma resonances and integrated optical structures is discussed extensively, as is the use of ellipsometry. Discussion of the spectroscopies used is broken into a section on electronic spectroscopies and an extensive discussion of vibrational spectroscopies. Vibrational information may be obtained with photons (absorption or scattering) or electrons (loss spectra), and the types of experimental systems amenable to each, along with the advantages and disadvantages of each are explored. 相似文献