Inductive-resonant triplet-triplet annihilation in solid solutions of erythrosine

Experimental investigations of annihilation-induced delayed fluorescence and phosphorescence of frozen ethylene glycol solutions activated by erythrosine were carried out. It is found that the kinetics of the annihilation-induced delayed fluorescence is nonexponential in the initial stage, and approaches an exponential decay at later stages with the lifetime equal to half the triplet-state lifetime. It is shown that experimental data agree well with the theory proposed to describe triplet-triplet annihilation by an inductive-resonant mechanism in solid solutions of complex organic molecules. Belarusian State University, 4, F. Skorina Ave., Minsk, 2200050, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 5, pp. 629–632, September–October, 1997.     

Heterogeneous triplet-triplet annihilation of erythrosine and anthracene molecules on a fractal anodized aluminum surface

We have studied exchange resonance processes of homogeneous triplet-triplet annihilation and heterogeneous triplet-triplet annihilation for erythrosine and anthracene molecules on an anodized aluminum surface over a broad temperature range. We have shown that the kinetics of the considered processes are determined by the dimensionality of the molecular clusters on the porous anodized aluminum surface. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 2, pp. 205–210, March–April, 2007.     

Regularities of triplet-triplet annihilation of aromatic hydrocarbons in aqueous micellar solutions of sodium dodecyl sulfate

Investigation of deactivation processes in triplet states of a series of aromatic hydrocarbon molecules (antracene, 1,2-benzantracene, and 3,4-benzpyrene) made it possible to reveal the presence of triplet-triplet annihilation of the molecules in aqueous micellar solutions of sodium dodecyl sulfate. It is shown that the effect of microheterogeneous solutions on the process of triplet-triplet annihilation manifests itself in an increase in the probability of excimerization upon dissociation of triplet pairs of 1,2-benzantracene and 3,4-benpyrene molecules compared to one-component solutions. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 5, pp. 626–628, September–October, 1997.     

Determination of the rate constants of excited-complex formation and the diffusion rate constants for triplet-triplet annihilation kinetics for tetrapyrrole molecules in liquid solutions

With the flash-photolysis method, the kinetis of triplet-triplet annihilation (TTA) is investigated for a number of tetrapyrrole molecules in liquid solutions. Based on the analysis of the kinetic scheme of TTA through the formation of excited complexes (TT) a procedure for determining the constant of the rate of (TT) formation from two molecules in the triplet state (k₁) is proposed. The k₁ values obtained are equal to the rate constants for the processes controlled by molecular diffusion in the solution (K_d), which are calculated by a modified Vavilov-Debye formula. The values of K_d can be determined experimentally by the proposed procedure for processing the data on TTA. Institute of Molecular and Atomic Physics, National Academy of Sciences of Belarus, 70, F. Skorina Ave., Minsk, 220072. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 4, pp. 521–527, July–August, 1998.     

Fluorescence quenching of water-soluble porphyrins by molecular oxygen

Quenching by molecular oxygen of excited states of water-soluble anionic 5,10,15,20-tetarkis-(4-sulfonatophenyl)-porphyrin (H₂TSPP) and cationic 5,10,15,20-tetrakis-(4-N-methylpyridyl)-porphyrin (H₂TMPyP) in aqueous ethanol was investigated. It was found that fluorescence quenching of dissociated (in water) and undissociated (in ethanol) forms of H₂TSPP was diffusion-controlled and occurred at distances close to contact ones (0.5–0.8 nm). Fluorescence of the dissociated form of H₂TSPP was quenched with rate constant k_S that was 1.7 times greater than that of the undissociated form. It was proposed that this was due to a decrease in the porphyrin molecule oxidation potential on going from the undissociated to the dissociated form. It was shown that the most probable reason for the dramatic increase in the rate constant of the fluorescence quenching of H₂TMPyP in water compared with that of H₂TSPP was the low-lying intramolecular charge-transfer state typical of H₂TMPyP. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 2, pp. 170–176, March–April, 2008.     

Homo- and Heteroannihilation of Triplet-Excited Bengali Rose and Anthracene Molecules on Silica in a Wide Temperature Range

The processes of triplet-triplet annihilation of the triplet-energy donor of Bengali rose dye and anthracene acceptor adsorbed on the surface of wide-pore silica have been investigated in the temperature range 150–290 K. The rate constants of homo- and heteroannihilation of the molecules of luminophors have been determined in a wide temperature range. It has been established that the processes of energy transfer in the initial (after photoexcitation) periods of phosphorescence decay are described by the Inokuti–Hirayama equations modified in the present work for a two-dimensional problem, whereas in the mean-time and long-time periods the kinetics of phosphorescence decay becomes similar to the fractal one.     

Kinetics of Triplet-Triplet Annihilation in Organic Glasses

In the present paper, the results of the investigation of the decay kinetics of delayed luminescence of organic glasses are presented. A strong deviation of the decay of both phosphorescence and annihilation delayed fluorescence from the exponential law is observed. This effect is shown to be due to the relaxation process of electronic excitation energy in the system with large energetic disorder. At the same time, the presence of two time intervals in which the rate coefficient for triplet-triplet annihilation (TTA) reaction shows different dependence on time is observed. On a short time scale the classical behavior is observed, i.e., the reaction is well described by the second-order equation with a time-independent rate coefficient. At the limit of long times, we have strong dependence of rate coefficient on time, i.e., the electronic excitation energy transport is dispersive. It is shown that behavior observed for the rate coefficient for TTA reaction is due to the relaxation process (on short time scale) and the equilibrium energy migration (in long time limit).     

苯甲酸及其甲基取代物的激光光解研究

研究了苯甲酸及其甲基取代物在248 nm激光作用下的光电离及光激发行为,测定了光电离量子产额和激发三线态寿命及其自猝灭速率常数。实验结果显示甲基在苯环不同位置的取代对苯甲酸化合物激发三线态的影响不明显。利用分步双激光技术对苯甲酸激发态进行共振激发,对可能生成的瞬态产物进行了初步探讨。     

Kinetics of Triplet-Triplet Annihilation of Mg-Phthalocyanine in Methanol and Deuteromethanol

Using the method of flash photolysis, the effect of deuteration of a solvent on the kinetics of triplet-triplet annihilation is studied on the example of Mg-phthalocyanine (Mg-Phc) in methanol-h ₄ and methanol-d ₄ at 298 K. The time and concentration kinetic dependences are different in different solvents, which cannot be explained only by the difference in the viscosity of the latter. The experimental data are analyzed based on consideration of the triplet-triplet annihilation mechanism via the formation of triplet-triplet complexes from molecules in a triplet state. It is established that in methanol-d ₄ the constants of the rates of monomolecular deactivation of the triplet state and of the decomposition of the complexes is 1.5–2 times smaller than in methanol-h ₄. The effect of deuteration is explained by the decrease in the rate of dipole-dipole energy transfer from the triplet state of the pigment to the solvent molecules in deuteration.     

Relationship between the diffusion rate constant and rate constant of triplet-triplet annihilation for porphyrins in liquid solutions

Institute of Molecular and Atomic Physics, Academy of Sciences of Belarus, 70. F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 63, No. 4, pp. 613–621, July–August, 1996.     

Delayed Luminescence of 8-Aza-D-Homogone-1,3,5(10),13-Tetraene-12,17a-Dione in the Gas Phase and Solid Solutions

It is shown that the delayed-luminescence spectrum of 8-aza-D-homogone-1,3,5(10),13-tetraene-12,17a-dione (8-aza-D-homogonane) in the gas phase comprises a band of thermally activated delayed fluorescence and a band of annihilation delayed fluorescence that are respectively due to the C- and D-centers representing products of photo-and thermotransformations of the initial steroid for which we failed to detect delayed luminescence. The triplet-triplet energy transfer from the C-centers to the D-centers has been detected and its efficiency has been determined. It has been established that, in a frozen hexane solution (T = 77 K) of the substance taken from a vacuum cuvette after the investigation of initial 8-aza-D-homogonane in the gas phase, only the C- and D-centers phosphoresce. For a frozen solution of the initial steroid in a vitrifying mixture of tetrahydrofuran and toluene, a phosphorescence of both the steroid itself (λ _max ^phos = 415 nm) and the C- and D-centers (λ _max ^phos = 498 and 532 nm, respectively) was detected. This indicates that even the initial steroid kept at room temperature contains products of its transformation whose concentration increases on irradiation and heating. The C- and D-centers are stable molecules.__________Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 2, pp. 192–197, March–April, 2005.     

Long-lived luminescence of complex molecules

Results of investigations of all types of long-lived luminescence of organic molecules in the gas phase and condensed media are presented. Methods for identification and separation of contributions of phosphorescence and thermally activated fluorescence in long-lived luminescence of organic-molecule vapors are proposed. Energy transfer and migration processes in the case of the inductive-resonant mechanism of intermolecular interaction leading to the appearance of sensitized phosphorescence and annihilation-induced delayed fluorescence are considered. Experimental results on energy migration obtained for solid solutions of organic compounds are analyzed within the framework of the concepts of percolation theory with account for the microscopic inhomogeneity of the systems under investigation and the fractal properties of the clusters of activator molecules. Institute of Molecular and Atomic Physics, National Academy of Sciences of Belarus, F. Skorina Ave., 70, Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 5, pp. 662–674, September–October, 1998.     

Delayed fluorescence of porphyrins in different media

Lifetimes of TPPS₄ (meso-tetraphenylporphine tetrasulfonate) triplet states were measured for liquid solutions of different acidity and viscosity and as a function of acceptor concentration for different acceptors (bovine serum albumin, tryptophan and furfuryl alcohol). Triplet lifetimes were estimated by monitoring the decay of TPPS₄ delayed fluorescence of E-type. The lifetime of delayed fluorencence depends on the concentration of O₂, since the latter is an effective quencher of the triplet state. The lifetime is shown to be influenced mainly by degree of aggregation state of TPPS₄ and, therefore, by the pH of the solution, decreasing with pH and for each pH remaining constant over a wide range of acceptor concentrations. The monomeric species is found to have the longest triplet lifetime in aqueous phosphate-buffered saline solution at neutral pH, especially when bound to albumin, despite of the low viscosity and protonated nature of the medium.     

Effect of low radiation doses on the content of endogeneous porphyrins in the living organism

Investigations of urinary excretion of copro- and uroporphyrins from the organism of healthy humans and humans exposed to low radiation doses (children and adolescents, adults and pregnant females) have been performed with the use of the high-sensitivity fluorescence method of determination of endogeneous porphyrins in the living organism. The ranges of the most probable concentrations of copro- and uroporphyrins in the morning portion of urine were determined for three control groups of healthy humans and six test groups of humans exposed to low radiation doses. It was established that the concentration of endogeneous porphyrins excreted from the organism of adults subjected to the action of ionizing radiation is significantly decreased as compared with the norm and that living for a long time in radionuclidecontaminated territories leads to steady disturbances of porplyrin excretion from the organism. It was also established that the concentration of endogenous porphyrins excreted from the organism of children and adults evacuated from the radionuclide-contaminated zone is significantly increased as compared with the norm. Reported at the VIIIth International Conference on Spectroscopy of Porphyrins and Their Analogs, Minsk, September 22–26, 1998. Institute of Molecular and Atomic Physics, National Academy of Sciences of Belaus, 70, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 4, pp. 545–548, July–August, 1999.     

Absolute reactivity of arylallyl carbocations

A series of α‐vinyl arylmethyl cations were generated and studied using nanosecond laser flash photolysis. Rate constants for the decay of the substituted α‐vinyl arylmethyl cations were determined under solvolytic conditions in pure solvents and solvent mixtures of 1,1,1,3,3,3‐hexafluoro‐2‐propanol (HFIP) and 2,2,2‐trifluoroethanol (TFE). In addition the absolute reactivity of the carbocations with added nucleophiles were obtained. The reactivities of the α‐vinyl arylmethyl cations were then compared to the reactivities of the corresponding α‐methyl, α‐phenyl, and α‐cyclopropyl arylmethyl cations. Hammett σ⁺ plots of each of the series of carbocations were obtained and the substituent effects on carbocation reactivity analyzed. These data show that the influence of substituent on the reactivity of the α‐vinyl carbocations was different from the substituents effects on the reactivity of the α‐methyl, α‐phenyl, and α‐cyclopropyl series. Copyright © 2008 John Wiley & Sons, Ltd.     

Broadening of triplet-triplet absorption band in molecular structures with different spatial dimensionalities

Within the framework of a dipole approximation, the form of the light absorption band for exciton transitions between triplet zones in one-, two-, and three-dimensional periodic molecular structures is calculated. Allowance is made for exciton attenuation as a frequency-independent parameter. The analytical expressions obtained make it possible to analyze the band for molecular structures of different spatial dimensionalities as a function of the difference in bandwidths, attenuation, and lattice temperature. Institute of the Surface Chemistry, National Academy of Sciences of Ukraine, 31, Nauka Ave., Kiev 252022, Ukraine. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 5, pp. 586–590, September–October, 1997.     

Phototransformation mechanism of monuron induced by the triplet benzophenone in aqueous solution

Phototransformation mechanism of monuron induced by the triplet benzophenone in aqueous solution was investigated by laser flash photolysis technique, while quenching of the triplet benzophenone by monuron was studied by nanosecond transient absorption spectroscopy. The transient species in the transient absorption spectra have been identified by quantum chemistry calculations. The results show that under 355‐nm irradiation proton transfer between the triplet benzophenone and monuron happens, and monuron radical is formed and followed by dechlorination degradation reactions. This work indicated that in aqueous solution some dissolved natural organic matters are helpful to degradation of the organic pollutants under the sunlight. Copyright © 2015 John Wiley & Sons, Ltd.