排序方式: 共有9条查询结果,搜索用时 281 毫秒
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S. L. Bondarev V. N. Knyukshto S. A. Tikhomirov I. I. Kalosha D. N. Bobrov N. V. Masalov N. M. Nevar V. I. Tyvorskii A. V. Kel'in O. G. Kulinkovich K. Dziliński 《Journal of Applied Spectroscopy》2002,69(2):230-237
By the methods of luminescence, picosecond spectroscopy, and quantumchemical calculations the mechanisms of electron excitation energy deactivation in some oligothiophenes with intramolecular charge transfer depending on the solvent polarity and viscosity have been investigated. While for 2Npiperidino5(2,2dicyanovinyl)thiophene (PDCVT) the main channel of nonradiative deactivation is the transition to a lower intermediate state with a twisted double bond controlled by the medium viscosity, in the case of (E){2[25piperidino2thienyl]6(trifluoridemethyl)4H4pyranylidene}propanedinitryl (PTFDN) fluorescence quenching is initiated by the solvent polarity. For two other oligothiophenes, 2Npiperidino5cyanothiophene (PCT) and 2Npiperidino5cyanoterthiophene (PCTT), differing in the length of the thiophene chain, we have revealed, along with the effective quenching of fluorescence in shortchain PCT (independent of the solvent polarity and viscosity), an increase in the radiation capacity in PCTT with increasing polarity of the solvent. The possible mechanisms of nonradiative deactivation in the investigated oligothiophenes are discussed. 相似文献
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R Nirmala V Sankaranarayanan K Sethupathi AV Morozkin T Geethakumary Y Hariharan 《Pramana》2002,58(5-6):1101-1104
New R
2Ti3Ge4 (R=Dy, Ho and Er) intermetallic compounds have been synthesized and characterized by X-ray diffraction and low temperature ac
magnetic susceptibility, electrical resistivity and thermoelectric power measurements were carried out. The compounds crystallize
in the parent, Sm5Ge4-type orthorhombic structure (space group Pnma) and lanthanide contraction is observed as one moves along the rare-earth series.
The changeover from paramagnetic to antiferromagnetic phase happens at low temperatures and the ordering temperature scales
with the de Gennes factor. The electrical resistivity is metallic with a negative curvature above 100 K. Thermopower displays
a weak maximum at temperatures less than 50 K signifying the possible phonon and magnon drag effects. 相似文献
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A mild, general, and efficient method for the synthesis of 2-monosubstituted and 2,5-disubstituted furans via the CuI-catalyzed cycloisomerization of alkynyl ketones was developed. It was demonstrated that furans containing both acid- and base-labile groups could be easily synthesized using this methodology. A plausible mechanism for this transformation is proposed. 相似文献
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Dudnik AS Sromek AW Rubina M Kim JT Kel'in AV Gevorgyan V 《Journal of the American Chemical Society》2008,130(4):1440-1452
A general, mild, and efficient 1,2-migration/cycloisomerization methodology toward multisubstituted 3-thio-, seleno-, halo-, aryl-, and alkyl-furans and pyrroles, as well as fused heterocycles, valuable building blocks for synthetic chemistry, has been developed. Moreover, regiodivergent conditions have been identified for C-4 bromo- and thio-substituted allenones and alkynones for the assembly of regioisomeric 2-hetero substituted furans selectively. It was demonstrated that, depending on reaction conditions, ambident substrates can be selectively transformed into furan products, as well as undergo selective 6-exo-dig or Nazarov cyclizations. Our mechanistic investigations have revealed that the transformation proceeds via allenylcarbonyl or allenylimine intermediates followed by 1,2-group migration to the allenyl sp carbon during cycloisomerization. It was found that 1,2-migration of chalcogens and halogens predominantly proceeds via formation of irenium intermediates. Analogous intermediate can also be proposed for 1,2-aryl shift. Furthermore, it was shown that the cycloisomerization cascade can be catalyzed by Br?nsted acids, albeit less efficiently, and commonly observed reactivity of Lewis acid catalysts cannot be attributed to the eventual formation of proton. Undoubtedly, thermally induced or Lewis acid-catalyzed transformations proceed via intramolecular Michael addition or activation of the enone moiety pathways, whereas certain carbophilic metals trigger carbenoid/oxonium type pathway. However, a facile cycloisomerization in the presence of cationic complexes, as well as observed migratory aptitude in the cycloisomerization of unsymmetrically disubstituted aryl- and alkylallenes, strongly supports electrophilic nature for this transformation. Full mechanistic details, as well as the scope of this transformation, are discussed. 相似文献
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Resonant ultrasound spectroscopy was used to measure the elastic constants of bcc Ta0.33V0.67 over the temperature range 3.5–300?K; the results were compared to earlier measurements on C15 TaV2. The temperature dependence of the polycrystalline shear modulus is completely different in the two phases; that of the bcc phase decreases with temperature whereas that of the C15 phases increases in an anomalous fashion. This difference is consistent with a model involving doubly-degenerate levels at the X point of the Brillouin zone in the C15 phase with the Fermi level lying near the doubly degenerate level. This model accounted for the unusual behaviour of the C15 phase. Debye temperatures were determined from the ultrasonic measurements: 295?K for the C15 phase and 315?K for the bcc phase. 相似文献
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