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1.
The occurrence of two noninteracting forms of Pd-porphin in the ground electronic state in a wide number of Shpolskii matrices maintained at liquid helium temperature was observed with the help of the finestructure phosphorescence spectra of these systems. The ratio between these forms can be varied in wide limits by choosing a particular matrix, which indicates that the matrix plays a significant role in the conformation formation of the tetrapyrrole macrocycle. Based on comparison both with the resonance Raman spectra and with the results of investigations of metal complexes of porphin by the selective spectroscopy methods, the shortwavelength spectral form has been shown to correspond to the planar molecular structure, whereas the longwavelength form has been attributed to a nonplanar molecular structure with the distortion of the porphin macrocycle of the saddle type. The results obtained indicate that the methods of fine structure spectroscopy make it possible to efficiently study distorted molecular structures stabilized in solid matrices at low temperatures. 相似文献
2.
Fine-structure vibronic fluorescence spectra of meso-substituted porphyrins and their interpretation
L. L. Gladkov A. S. Starukhin A. M. Shul'ga I. V. Stanishevskii 《Theoretical and Experimental Chemistry》1991,26(6):623-627
Fine-structure fluorescence spectra have been recorded on selective laser excitation at 4.2 K for meso-tetraethylporphyrin (TEP), meso-tetrapropyl-porphyrin (TPP) and their derivatives with deuteriated NH groups. An interpretation of the spectra obtained is proposed on the basis of calculations of the normal vibrations of the molecules. It was noted that the interaction of the ethyl groups of TEP with the solvent leads to different orientations of these groups to the plane of the macrocycle, which leads to an increase in the number of lines in the frequency range 150–400 cm–1 and to their broadening.Translated from Teoreticheskie i Éksperimental'naya Khimiya, Vol. 26, No. 6, pp. 664–668, November–December, 1990. 相似文献
3.
We have studied the temperature dependence of the radiative deactivation of the Pd-porphine triplet states in Shpol’skii matrices
in the temperature range 1.2–210 K. A substantial transformation of the phosphorescence spectra is observed as the temperature
increases and is due to the inclusion of thermally activated Pd-porphine states in the radiative deactivation processes. The
activation energy Ea of these Pd-porphine states is measured in matrices of n-octane and n-nonane. The splitting of the lowest quasidegenerate
triplet state ΔE(T2−T1) is determined for planar and distorted conformations of the Pd-porphine macrocycle in the n-octane matrix as 40 and 57 cm−1, respectively. The ability to use the temperature dependence of the phosphorescence properties of Pd-porphine to fabricate
molecular thermometers for the low-temperature range is analyzed.
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Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 4, pp. 460–464, July–August, 2007. 相似文献
4.
Institute of Molecular and Atomic Physics, Academy of Sciences of Belarus, 70, F. Skorina Ave., Minsk, 220072, Belarus. Translated
from Zhurnal Prikladnoi Spektroskopii, Vol. 62, No. 2, pp. 137–144, March–April, 1995. 相似文献
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We study the temperature dependence of the radiative deactivation of triplet states of Pdand Pt-porphin molecules in n-alkane matrices in the temperature range 4.2–210 K. The nature of the thermally activated “hot” lines that are observed in
phosphorescence spectra of Pdand Pt-porphin is discussed in detail. We show that, because of the degeneracy lifting of the
triplet state T
1, 2 in the crystal field of n-alkane matrices, lines of the transitions T1 → S
0 and T
2 → S
0 are spectrally spaced and, in all cases, the T
2 state is the first state that is activated with increasing temperature. We analyze the dependences of the T
2-T
1 splitting on the chelated metal ion and the type of the matrix. The possibility of measuring cryogenic temperatures with
molecular thermometers that use the thermochromic properties of Pdand Pt-porphin in n-alkane matrices is discussed. 相似文献
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