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O. S. Filipenko S. M. Aldoshin G. V. Shilov N. I. Makarova V. A. Kharlanov M. I. Knyazhanskii 《Russian Chemical Bulletin》1995,44(2):287-292
The molecular structures of the initial compounds and the products of photocyclization involving amino and azomethine groups in perchlorates ofN-amino (1) andN-azomethine (2) derivatives of 2,4,6-triphenylpyridinium cations were studied. Cations1 and2 have an essentially non-coplanar arrangement of the -Ph rings, and the product of photocyclization of2, cation3, is characterized by a flattened structure. It was found that the orientation of the lone electron pair of the N atom with respect to one of the planes of the -Ph rings in molecule1 is more favorable for monocyclization involving the amino group. The structure of molecule2 allows two routes of the photoreaction,viz., O N proton transfer and monocyclization with an -Ph ring. However, the structural features of molecule2 are more favorable for photocyclization.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 296–301, February, 1995. 相似文献
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Yu. P. Andreichikov M. I. Knyazhanskii Ya. R. Tymyanskii G. E. Trukhan G. N. Dorofeenko 《Chemistry of Heterocyclic Compounds》1974,10(6):696-698
The electronic spectra of a number of benzylidene derivatives of N-aminoarylpyridinium perchlorates are associated with absorption localized on the individual pyridinium and azomethine fragments and with intramolecular charge transfer (ICT) from the azomethine fragment to the pyridinium ring. The luminescence is associated with the latter process. The photochromism is due to proton transfer in the excited state of the azomethine fragment, which competes with ICT, and is also due to structural factors. 相似文献
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A. V. Metelitsa N. V. Volbushko M. I. Knyazhanskii 《Chemistry of Heterocyclic Compounds》1991,27(4):357-362
Diabatic photoinduced ring opening of the chromene ring of 2-amino-5,6-benzo-2H-chromenes and 2-amino-6-methyl-7,8-benzo-2H-chromenes leads, in the same way as a thermally induced reaction, to the establishment of ring-chain tautomer equilibrium in the ground electronic state, the position of this equilibrium depending on the polarity of the solvent, the temperature, and structural factors. o-Quinoid tautomers exist as several stable isomeric forms: an acoplanar cis-S-cis-trans-form absorbing in the shortwave region, and S-trans-isomers absorbing in the longwave region of the spectrum. Photoexcitation of the o-quinoid forms in the temperature range 125–190 K initiates mutual conversions of these and the initial 2H-chromene structure. The relative stability of the conformers of the o-quinoid form depends on steric and electronic factors: benzanellation in positions 5,6 leads to stabilization of the cis-S-cis-trans-isomer and in positions 7,8 the S-trans-isomers are more preferred: -acceptor substituents on the amine component increase the stability of the cis-S-cis-trans isomer and electron-donor substituents stabilize the S-trans-isomer.Communication 20 from the series Photo- and thermochromic piranes. See [1] for Communication 19.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 453–458, April, 1991. 相似文献
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A. V. Metelitsa M. I. Knyazhanskii N. V. Volbushko I. Yu. Grishin Yu. M. Chunaev N. M. Przhiyalgovskaya 《Chemistry of Heterocyclic Compounds》1991,27(9):1012-1015
Only E Z isomerization is observed for the steady irradiation of fulgides based on 1,2-dimethyl-3-formylindole in contrast to the analogs based on 3-acetylindole. The formation of cyclic photoisomers is registered by the method of impulse photolysis. The presence of a methyl substituent in the position 2 of the indole portion leads to a significant increase in the stability of the photochromic system. The introduction of alternative reaction centers of cyclization in the form of bulky phenyl groups leads to the suppression of electrocyclization at the position 2 of the indole portion and the formation of dihydronaphthalene structures.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1255–1258, September, 1991. 相似文献
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Ya. R. Tymyanskii V. M. Feingel'man M. I. Knyazhanskii N. V. Kholodova 《Chemistry of Heterocyclic Compounds》1984,20(11):1262-1266
The spectral-fluorescent and photochemical properties of 1-naphthyl-2,4-di- and 2,4,6-triphenylpyridinium perchlorates were investigated in solutions at 293 and 77 °K. The anomalously large Stokes shift of the fluorescence was due to the adiabatic change in the structure of the molecules as a result of rotations of the C- or N-aryl substituents. The observed phosphorescence arises as a result of intramolecular T-T transfer of energy to the N-naphthyl radical. 1-Naphthyl-2,4-diphenylpyridinium cations are capable of photocyclization with the formation of intensely fluorescent derivatives of benzo[b or c]pyrldo[1,2-f]phenanthridinium, isolated with high yields in preparative photolysis.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1528–1532, November, 1984. 相似文献
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M. S. Chernov’yants E. B. Podgornaya A. V. Chernyshev A. V. Metelitsa M. O. Knyazhanskii 《Journal of Analytical Chemistry》2000,55(3):245-248
A method for the identification of organic triiodides is proposed, and rapid, highly sensitive procedures for the extraction-spectrophotometric
and extraction-fluorometric determination of medicinal preparations as ion associates with hydroxyxanthene (Eosin) and triphenylmethane
(Bromothymol Blue) dyes. The formation of 1 : 1 ion associates with an absorption maximum at 545 nm (430 nm for ion associates
with Bromothymol Blue) and a fluorescence maximum at 560 nm was detected. The ion associates were extracted with chloroform
from a water-ethanol solution at pH 6.86 and 9.18. The detection limits were cmin ≈ 4.3 × 10-7 M for the extraction-spectrophotometric and cmin ≈ 8.6 sx 10-8 M for the extraction-fluorimetric procedure; RSD ≤2%. The developed procedures can be used for controlling medicinal preparations
and monitoring biological materials 相似文献
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Ivakhnenko T. E. Makarova N. I. Ivakhnenko E. P. Chuev I. I. Aldoshin S. M. Minkin V. I. Knyazhanskii M. I. 《Russian Chemical Bulletin》2000,49(12):1981-1987
New photochromic compound 1-p-tolylsulfonylazo-2,4,6,8-tetrakis(tert-butyl)phenoxazine containing the intramolecular hydrogen bond NH...N and the corresponding model structures 2,4,6,8-tetrakis(tert-butyl)-1-(veratroylazo)phenoxazine and 2,4,6,8-tetrakis(tert-butyl)-N-acetyl-1-(p-tolylsulfonylazo)phenoxazine were synthesized and studied. The data obtained suggested the mechanism of the photoreaction resulting in the accumulation of betaine 1-hydroxy-2,4,6,8-tetrakis(tert-butyl)-10-tolylsulfonylphenoxazin-9-one. The photochromic transformations in the molecule under study are due to intramolecular proton phototransfer followed by E–Z-isomerization about the N–N bond and the formation of betaine 1-hydroxy-2,4,6,8-tetrakis(tert-butyl)-10-tolylsulfonylphenoxazin-9-one. The molecular and crystal structure of the photoproduct was studied by X-ray analysis. 相似文献