Dichroism of absorption and polarization of phosphorescence of closed form of nitro-substituted indoline spiropyrans

Khamchukov, Yu. D.; Luchina, V. G.; Gradyushko, A. T.; Marevtsev, V. S.; Lyubimov, Alexander V.; Cherkashin, Μ. I.

doi:10.1007/bf00664536

J Appl Spectrosc

1990

DOI: 10.1007/bf00664536

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Dichroism of absorption and polarization of phosphorescence of closed form of nitro-substituted indoline spiropyrans

Yu. D. Khamchukov

V. G. Luchina

A. T. Gradyushko

et al.

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Cited by 2 publications

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“…In [1], the results of a purely empirical investigation of their vibrational spectra are presented. It is known that photochromic processes proceed with participation of vibrational and vibronic states [1,2]. Therefore, the practical creation of photochromic materials based on the molecules of spirocompounds requires the study of vibrational and vibronic states.…”

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Vibrational Spectra of the Closed Form of a Molecule of Indoline Spiroanthraceneoxazine

et al. 2005

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In an approximation of the generalized valence force field, the frequencies and forms of the normal vibrations of the free molecule of spiroanthraceneoxazine (SAO) are calculated. The vibrational spectra of SAO are measured: the IR absorption spectra in an NaCl disk and the Raman spectra in a KBr disk. The calculated and experimental data were correlated with the aid of a method of refined initial data. The results obtained agree with the calculated and experimental spectra of model and related compounds.Keywords: vibrational spectroscopy, generalized valence force field of a molecule.Introduction. The literature devoted to studying the photochromy of indoline spirocompounds completely lacks calculations of the normal vibrations of these compounds. In [1], the results of a purely empirical investigation of their vibrational spectra are presented. It is known that photochromic processes proceed with participation of vibrational and vibronic states [1,2]. Therefore, the practical creation of photochromic materials based on the molecules of spirocompounds requires the study of vibrational and vibronic states. An adequate solution of this problem is possible only by way of extensive theoretical and experimental investigation.In the present work, an attempt is made at a theoretical and experimental investigation of the normal vibrations of the free molecule of 1′,Computational and Experimental Techniques. SAO molecules were synthesized by the technique suggested in [3]. The frequencies and forms of normal vibrations of the free molecules were determined using the program of calculation of the frequencies and forms of normal vibrations in the approximation of the generalized valence force field. This approximation has been applied in an enormous number of works [see, e.g., [4][5][6]). The choice of the equilibrium nuclear configuration of the free molecule of SAO was made with the aid of the "OUP Molecular Modeling Package" program. The natural coordinates selected as well as valence and deformation ones are presented in Fig. 1. Proceeding from the validity of the condition of the transferrability of the force constants of identical nuclear groupings entering into different molecules [5] and from the literature data, we have selected the elements of the matrices of force constants. The first calculation of the frequencies and forms of the normal vibrations of SAO was performed on the basis of calculated parameters of the nuclear configuration of the free molecule and the force matrix elements selected from the literature data [6][7][8]. To attain a more precise agreement between the calculated and experimental frequencies, variation of the values of force constants was applied. Subjected to variation were the force constants of natural coordinates the changes in which yield the greatest contribution to the form of vibrations (potential energy distribution (PED)). Here, the geometric parameters of the molecule did not change. The difference of ν cal from ν exp was reduced to a value of the order of the accuracy value wi...

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Vibrational Spectra of the Closed Form of a Molecule of Indoline Spiroanthraceneoxazine

et al. 2005

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“…9 Stretching of polyethylene ffdrns, determination of the degree of dichroism, and calculations of the directions of the moments of electron transitions were carried out analogously to the procedure reported in Ref. 8 in which the dichroism of absorption of the initial form of the SBP molecule in polyethylene was studied. The corrected phosphorescence spectra, the phosphorescence polarization and excitation spectra, and the lifetime of the triplet state were measured in rectangular quartz cells on an instrument according to procedures reported previously.…”

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Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

1997

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The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene fdms and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom.Key words: spirobenzopyrans, phosphorescence, polarization, dichroism.The 1,3,3-trimethyl-6 "-nitrospiro(indoline-2,2 "-[2H-1]benzothiopyran) (STP) molecule exhibits pronounced photochromic properties. When irradiated with UV light, for example, the STP molecule is transformed from the initial state A into the colored form B, which absorbs light intensely in the visible region of the spectrum. In studies of STP, the colored form B has recieved the most attention, 1-5 because this form is characterized by a substantially larger bathochromic shift of the maximum of the long-wavelength absorption than the oxygen-containing analog, namely, nitrospirobenzopyran (SBP). However, replacement of the O atom in the benzopyran fragment of the spiro compound should also affect the photophysical and photochemical properties of the initial form A, which, in turn, should be seen in a change in the characteristics of the luminescence spectrum compared to those of the SBP molecule. The absorption and luminescence spectra of nitro-substituted spiro compounds consist generally of structureless overlapping bands, which are difficult to analyze. Therefore, the results of studies of the anisotropy of light absorption and emission are of importance. Based on these results, one can infer the nature of electron transitions and the orientations of their moments relative to the atomic core of the molecule as well as the mechanism of the spine Me NO 2 STP orbital interaction. In this work, we studied for the first time the dichroism of absorption of STP and the polarization of phosphorescence of the closed form of STP molecules in oriented polyethylene films and in solutions with different polarity, and compared our results with the data on its oxygen-containing analog, namely, SBP.S-s Experimental 1,3,3 -Trimethyl-6 "-nitrospiro(indoline-2,2 ' -[2/-/-I ]benzothiopyran) was synthesized and purified according to the known procedure. 4 Polyethylene was purified by extraction in boiling chloroform. The purities of the samples were confirmed by the absence of impurity luminescence. STP molecules were introduced into polyethylene according to a procedure reported previously. 9 Stretching of polyethylene ffdrns, determination of the degree of dichroism, and calculations of the directions of the moments of electron transitions were carried out analogously to the procedure reported in Ref. 8 in which the dichroism of absorption of ...

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Dichroism of absorption and polarization of phosphorescence of closed form of nitro-substituted indoline spiropyrans

Cited by 2 publications

References 5 publications

Vibrational Spectra of the Closed Form of a Molecule of Indoline Spiroanthraceneoxazine

Vibrational Spectra of the Closed Form of a Molecule of Indoline Spiroanthraceneoxazine

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

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