8 research outputs found
A Study of the Ligand Composition Change of the Eu3+ Chelate by Two-Stage Laser Excitation Luminescence and Computer Simulation of Kinetics
The europium(III)- tris(dibenzoylmethane)- triphenylphosphine oxide complex was studied in the polycrystalline state and in toluene at 298 K using the luminescence excitation method with two-stage rectangular pulses with decreasing intensity of stages. ΠΠΎΠΌΠΏΠ»Π΅ΠΊΡ Π΅Π²ΡΠΎΠΏΠΈΠΉ (III) - ΡΡΠΈ (Π΄ΠΈΠ±Π΅Π½Π·ΠΎΠΈΠ»ΠΌΠ΅ΡΠ°Π½)-ΡΡΠΈΡΠ΅Π½ΠΈΠ»ΡΠΎΡΡΠΈΠ½ΠΎΠΊΡΠΈΠ΄ ΠΈΡΡΠ»Π΅Π΄ΠΎΠ²Π°Π½ Π² ΠΏΠΎΠ»ΠΈΠΊΡΠΈΡΡΠ°Π»Π»ΠΈΡΠ΅ΡΠΊΠΎΠΌ ΡΠΎΡΡΠΎΡΠ½ΠΈΠΈ ΠΈ ΡΠΎΠ»ΡΠΎΠ»Π΅ ΠΏΡΠΈ 298 K Ρ ΠΈΡΠΏΠΎΠ»ΡΠ·ΠΎΠ²Π°Π½ΠΈΠ΅ΠΌ ΠΌΠ΅ΡΠΎΠ΄Π° Π²ΠΎΠ·Π±ΡΠΆΠ΄Π΅Π½ΠΈΡ Π»ΡΠΌΠΈΠ½Π΅ΡΡΠ΅Π½ΡΠΈΠΈ Π΄Π²ΡΡ
ΡΡΡΠΏΠ΅Π½ΡΠ°ΡΡΠΌΠΈ ΠΏΡΡΠΌΠΎΡΠ³ΠΎΠ»ΡΠ½ΡΠΌΠΈ ΠΈΠΌΠΏΡΠ»ΡΡΠ°ΠΌΠΈ ΡΠΎ ΡΠΏΠ°Π΄ΠΎΠΌ ΠΈΠ½ΡΠ΅Π½ΡΠΈΠ²Π½ΠΎΡΡΠΈ ΡΡΡΠΏΠ΅Π½Π΅ΠΉ
Determination of Rate Constants and the Mechanism of Phototransformations of Metalloporphyrins by Solving the Inverse Photokinetic Problem
ΠΠ΅ΡΠΎΠ΄Π°ΠΌΠΈ ΠΎΠ±ΡΠ°ΡΠ½ΠΎΠΉ ΠΊΠΈΠ½Π΅ΡΠΈΡΠ΅ΡΠΊΠΎΠΉ Π·Π°Π΄Π°ΡΠΈ ΠΈΡΡΠ»Π΅Π΄ΠΎΠ²Π°Π½Ρ ΠΊΠΈΠ½Π΅ΡΠΈΠΊΠΈ ΡΠ»ΡΠΎΡΠ΅ΡΡΠ΅Π½ΡΠΈΠΈ Π½Π΅ΠΊΠΎΡΠΎΡΡΡ
Π·Π°ΠΌΠ΅ΡΠ΅Π½Π½ΡΡ
Zn- ΠΈ Mg-ΠΏΠΎΡΡΠΈΡΠΈΠ½ΠΎΠ² Π² ΡΠ²Π΅ΡΠ΄ΡΡ
ΠΏΠΎΠ»ΠΈΠΌΠ΅ΡΠ½ΡΡ
ΠΏΠ»Π΅Π½ΠΊΠ°Ρ
ΠΏΡΠΈ Π²ΠΎΠ·Π±ΡΠΆΠ΄Π΅Π½ΠΈΠΈ Π΄Π²ΡΡ
ΡΡΡΠΏΠ΅Π½ΡΠ°ΡΡΠΌΠΈ ΠΏΡΡΠΌΠΎΡΠ³ΠΎΠ»ΡΠ½ΡΠΌΠΈ Π»Π°Π·Π΅ΡΠ½ΡΠΌΠΈ ΠΈΠΌΠΏΡΠ»ΡΡΠ°ΠΌΠΈ ΠΈ 293K. Fluorescence kinetics of some substituted Zn- and Mg-porphyrins in solid polymeric films upon excitation by two-step-wise rectangular laser pulses and at 293 K are studied by methods of the inverse kinetic problem
A Study of the Ligand Composition Change of the Eu3+ Chelate by Two-Stage Laser Excitation Luminescence and Computer Simulation of Kinetics
The uropium(III)- tris(dibenzoylmethane)- triphenylphosphine oxide complex was studied in the polycrystalline state and in toluene at 298 K using the luminescence excitation method with two-stage rectangular pulses with decreasing intensity of stages
Characterization of the T1 State of Porphyrin Molecules on the Basis of Numerical Modeling of Decrease and Increase of Fluorescence Intensity Kinetics
For a number of porphyrin molecules, it was shown that their excitation by light pulses of a rectangular step shape and a certain duration led to experimentally observed dynamical decrease and increase of fluorescence kinetics due to changes in the population of the lower (metastable) triplet T1 state
Π‘ΠΏΠ΅ΠΊΡΡΠ°Π»ΡΠ½ΠΎΠ΅ ΠΏΡΠΎΡΠ²Π»Π΅Π½ΠΈΠ΅ Π°Π³ΡΠ΅Π³Π°ΡΠΈΠΈ ΠΌΠΎΠ»Π΅ΠΊΡΠ» ΠΎΠΊΡΠ°ΠΊΠ°ΡΠ±ΠΎΠΊΡΠΈΡΡΠ°Π»ΠΎΡΠΈΠ°Π½ΠΈΠ½Π° ΠΈ Π΅Π³ΠΎ ΡΠΈΠ½ΠΊΠΎΠ²ΠΎΠ³ΠΎ ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΠ° Π² Π½Π°Π½ΠΎΠΏΠΎΡΠΈΡΡΠΎΠΉ ΡΠΈΠ»ΠΈΠΊΠ°ΡΠ½ΠΎΠΉ Π³Π΅Π»Ρ-ΠΌΠ°ΡΡΠΈΡΠ΅
ΠΡΡΠ»Π΅Π΄ΠΎΠ²Π°Π½Ρ ΡΠΏΠ΅ΠΊΡΡΠ°Π»ΡΠ½ΠΎ-Π»ΡΠΌΠΈΠ½Π΅ΡΡΠ΅Π½ΡΠ½ΡΠ΅ ΡΠ²ΠΎΠΉΡΡΠ²Π° ΠΌΠΎΠ»Π΅ΠΊΡΠ» 2,3,9,10,16,17,23,24-ΠΎΠΊΡΠ°ΠΊΠ°ΡΠ±ΠΎΠΊΡΠΈ-ΡΡΠ°Π»ΠΎΡΠΈΠ°Π½ΠΈΠ½Π° ΠΈ Π΅Π³ΠΎ ΡΠΈΠ½ΠΊΠΎΠ²ΠΎΠ³ΠΎ ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΠ°, Π²Π½Π΅Π΄ΡΠ΅Π½Π½ΡΡ
Π² Π½Π°Π½ΠΎΠΏΠΎΡΠΈΡΡΡΠ΅ ΡΠΈΠ»ΠΈΠΊΠ°ΡΠ½ΡΠ΅ Π³Π΅Π»Ρ-ΠΌΠ°ΡΡΠΈΡΡ. Π£ΡΡΠ°Π½ΠΎΠ²Π»Π΅Π½ΠΎ, ΡΡΠΎ Π½Π° Π½Π°ΡΠ°Π»ΡΠ½ΠΎΠΉ ΡΡΠ°Π΄ΠΈΠΈ ΡΠΎΡΠΌΠΈΡΠΎΠ²Π°Π½ΠΈΡ ΡΠΈΠ»ΠΈΠΊΠ°ΡΠ½ΠΎΠ³ΠΎ ΠΊΠ°ΡΠΊΠ°ΡΠ° ΠΎΠ±ΡΠ°Π·ΡΡΡΡΡ Π-Π°Π³ΡΠ΅Π³Π°ΡΡ ΠΈΡΡΠ»Π΅Π΄ΡΠ΅ΠΌΡΡ
ΡΡΠ°Π»ΠΎΡΠΈΠ°Π½ΠΈΠ½ΠΎΠ². ΠΠ±Π½Π°ΡΡΠΆΠ΅Π½ ΡΡΡΠ΅ΠΊΡ Π²ΠΎΡΡΡΠ°Π½ΠΎΠ²Π»Π΅Π½ΠΈΡ ΠΌΠΎΠ½ΠΎΠΌΠ΅ΡΠ½ΠΎΠΉ ΡΠΎΡΠΌΡ ΡΠΈΠ½ΠΊΠΎΠ²ΠΎΠ³ΠΎ ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΠ° Π² Π³Π΅Π»Ρ-ΠΌΠ°ΡΡΠΈΡΠ΅ Π² ΠΏΡΠΎΡΠ΅ΡΡΠ΅ ΡΡΡΠΊΠΈ ΡΠΈΠ»ΠΈΠΊΠ°ΡΠ½ΠΎΠ³ΠΎ ΠΌΠ°ΡΠ΅ΡΠΈΠ°Π»Π°. ΠΠ±ΡΡΠΆΠ΄Π°ΡΡΡΡ ΠΏΡΠΈΡΠΈΠ½Ρ ΡΠ°Π·ΡΡΡΠ΅Π½ΠΈΡ Π°Π³ΡΠ΅Π³Π°ΡΠΎΠ² Π² ΠΎΠ³ΡΠ°Π½ΠΈΡΠ΅Π½Π½ΠΎΠΌ ΠΎΠ±ΡΠ΅ΠΌΠ΅ Π½Π°Π½ΠΎΡΠ°Π·ΠΌΠ΅ΡΠ½ΡΡ
ΠΏΠΎΡ ΠΌΠ°ΡΡΠΈΡΡ
Π‘ΠΏΠ΅ΠΊΡΡΠ°Π»ΡΠ½ΡΠ΅ ΠΈ Π°Π³ΡΠ΅Π³Π°ΡΠΈΠΎΠ½Π½ΡΠ΅ ΡΠ²ΠΎΠΉΡΡΠ²Π° ΠΌΠΎΠ»Π΅ΠΊΡΠ» ΡΠ΅Π½ΠΈΠ»ΡΠΈΠΎΠ·Π°ΠΌΠ΅ΡΠ΅Π½Π½ΡΡ Al-ΡΡΠ°Π»ΠΎΡΠΈΠ°Π½ΠΈΠ½ΠΎΠ² Π² Π½Π°Π½ΠΎΠΏΠΎΡΠΈΡΡΡΡ ΡΠΈΠ»ΠΈΠΊΠ°ΡΠ½ΡΡ ΠΌΠ°ΡΡΠΈΡΠ°Ρ
ΠΠ·ΡΡΠ΅Π½Ρ ΡΠΏΠ΅ΠΊΡΡΡ ΠΏΠΎΠ³Π»ΠΎΡΠ΅Π½ΠΈΡ, ΡΠ»ΡΠΎΡΠ΅ΡΡΠ΅Π½ΡΠΈΠΈ ΠΈ Π²ΠΎΠ·Π±ΡΠΆΠ΄Π΅Π½ΠΈΡ ΡΠ»ΡΠΎΡΠ΅ΡΡΠ΅Π½ΡΠΈΠΈ ΡΠ΅Π½ΠΈΠ»ΡΠΈΠΎΠ·Π°ΠΌΠ΅ΡΠ΅Π½Π½ΠΎΠ³ΠΎ Al-ΡΡΠ°Π»ΠΎΡΠΈΠ°Π½ΠΈΠ½Π° Π² ΡΠ°ΡΡΠ²ΠΎΡΠ°Ρ
, ΠΏΠ»Π΅Π½ΠΊΠ°Ρ
ΠΏΠΎΠ»ΠΈΠ²ΠΈΠ½ΠΈΠ»Π±ΡΡΠΈΡΠ°Π»Ρ ΠΈ ΠΌΠ°ΡΡΠΈΡΠ°Ρ
ΡΠΈΠ»ΠΈΠΊΠ°ΡΠ½ΡΡ
Π³Π΅Π»Π΅ΠΉ ΠΏΡΠΈ ΠΊΠΎΠΌΠ½Π°ΡΠ½ΠΎΠΉ ΡΠ΅ΠΌΠΏΠ΅ΡΠ°ΡΡΡΠ΅. Π£ΡΡΠ°Π½ΠΎΠ²Π»Π΅Π½ΠΎ, ΡΡΠΎ ΠΌΠΎΠ½ΠΎΠΌΠ΅ΡΠ½ΡΠ΅ ΡΠ»ΡΠΎΡΠ΅ΡΡΠ΅Π½ΡΠ½ΡΠ΅ ΡΠΎΡΠΌΡ ΠΏΡΠΈΠΌΠ΅ΡΠ½ΡΡ
ΠΌΠΎΠ»Π΅ΠΊΡΠ» ΠΎΠ±ΡΠ°Π·ΡΡΡΡΡ Π½Π΅ ΡΠΎΠ»ΡΠΊΠΎ Π² ΡΡΠ°Π½ΠΎΠ»Π΅ ΠΈ ΠΏΠΎΠ»ΠΈΠ²ΠΈΠ½ΠΈΠ»Π±ΡΡΠΈΡΠ°Π»Π΅, Π½ΠΎ ΠΈ Π² Π½Π΅ΠΎΡΠ³Π°Π½ΠΈΡΠ΅ΡΠΊΠΈΡ
ΠΈ ΠΎΡΠ³Π°Π½ΠΎ-Π½Π΅ΠΎΡΠ³Π°Π½ΠΈΡΠ΅ΡΠΊΠΈΡ
ΡΠΈΠ»ΠΈΠΊΠ°ΡΠ½ΡΡ
ΠΌΠ°ΡΡΠΈΡΠ°Ρ
, ΠΎΠΊΡΠ°ΡΠ΅Π½Π½ΡΡ
ΠΌΠ΅ΡΠΎΠ΄ΠΎΠΌ ΠΏΡΡΠΌΠΎΠ³ΠΎ Π·ΠΎΠ»Ρ-Π³Π΅Π»Ρ ΡΠΈΠ½ΡΠ΅Π·Π°. ΠΠΎΠΊΠ°Π·Π°Π½ΠΎ, ΡΡΠΎ ΠΏΡΠΈ ΠΎΠΊΡΠ°ΡΠΈΠ²Π°Π½ΠΈΠΈ ΡΠ΅ΡΡΠ°ΡΡΠΎΠΊΡΠΈΡΠΈΠ»Π°Π½ΠΎΠ²ΠΎΠΉ ΠΌΠ°ΡΡΠΈΡΡ ΠΌΠ΅ΡΠΎΠ΄ΠΎΠΌ ΠΈΠΌΠΏΡΠ΅Π³Π½Π°ΡΠΈΠΈ ΠΎΠ±ΡΠ°Π·ΡΡΡΡΡ Π½Π΅ΡΠ»ΡΠΎΡΠ΅ΡΡΠ΅Π½ΡΠ½ΡΠ΅ Π°Π³ΡΠ΅Π³Π°ΡΡ, ΠΏΡΠ΅Π΄ΠΏΠΎΠ»ΠΎΠΆΠΈΡΠ΅Π»ΡΠ½ΠΎ Π-ΡΠΈΠΏΠ°. ΠΠΎΠ»ΡΡΠ΅Π½Π½ΡΠ΅ ΡΠ²Π΅ΡΠ΄ΡΠ΅ ΡΠΈΠ»ΠΈΠΊΠ°ΡΠ½ΡΠ΅ ΠΌΠ°ΡΡΠΈΡΡ ΠΌΠΎΠ³ΡΡ Π±ΡΡΡ ΠΈΡΠΏΠΎΠ»ΡΠ·ΠΎΠ²Π°Π½Ρ Π² ΠΊΠ°ΡΠ΅ΡΡΠ²Π΅ ΡΠ½ΠΈΠ²Π΅ΡΡΠ°Π»ΡΠ½ΡΡ
Π»ΡΠΌΠΈΠ½Π΅ΡΡΠ΅Π½ΡΠ½ΡΡ
ΠΌΠ°ΡΠ΅ΡΠΈΠ°Π»ΠΎΠ² Π±Π»ΠΈΠΆΠ½Π΅Π³ΠΎ ΠΠ-Π΄ΠΈΠ°ΠΏΠ°Π·ΠΎΠ½Π°. The absorption, fluorescence, and fluorescence excitation spectra of phenylthio-substituted Al-phthalocyanine in solutions, polyvinyl butyral films, and silicate gel matrices at room temperature were studied. It was found that monomeric fluorescent forms of impurity molecules are formed not only in ethanol and polyvinyl butyral but also in inorganic and organic-inorganic silicate matrices colored by the direct sol-gel synthesis method. It was shown that nonfluorescent aggregates, presumably of the H-type, are formed when the tetraethoxysilane matrix is stained by the impregnation method. The obtained solid silicate matrices can be used as multipurpose luminescent materials for the near-IR region
Π₯Π°ΡΠ°ΠΊΡΠ΅ΡΠΈΡΡΠΈΠΊΠ° Π’1-ΡΠΎΡΡΠΎΡΠ½ΠΈΡ ΠΌΠΎΠ»Π΅ΠΊΡΠ» ΠΏΠΎΡΡΠΈΡΠΈΠ½ΠΎΠ² Π½Π° ΠΎΡΠ½ΠΎΠ²Π΅ ΡΠΈΡΠ»Π΅Π½Π½ΠΎΠ³ΠΎ ΠΌΠΎΠ΄Π΅Π»ΠΈΡΠΎΠ²Π°Π½ΠΈΡ ΠΊΠΈΠ½Π΅ΡΠΈΠΊΠΈ ΡΠ½ΠΈΠΆΠ΅Π½ΠΈΡ ΠΈ ΡΠ²Π΅Π»ΠΈΡΠ΅Π½ΠΈΡ ΠΈΠ½ΡΠ΅Π½ΡΠΈΠ²Π½ΠΎΡΡΠΈ ΡΠ»ΡΠΎΡΠ΅ΡΡΠ΅Π½ΡΠΈΠΈ
For a number of porphyrin molecules, it was shown that their excitation by light pulses of a rectangular step shape and a certain duration led to experimentally observed dynamical decrease and increase of fluorescence kinetics due to changes in the population of the lower (metastable) triplet T1 state. On the basis of exact analytical expressions for a three-energy-level model, a simple analytical relationships between the rate constants of intramolecular processes and experimentally measured parameters of the fluorescence kinetics were obtained. The three-dimensional isotropic orientation of the molecules in the framework of the chosen model was taken into account by numerical methods and allowed to simulate adequately the experimentally observed fluorescence kinetics. The T1 state lifetimes of the studied porphyrin molecules in polymer matrices were determined from experimental curves using numerical methods for solving inverse problems. The obtained values correlated with literature data. Features and advantages of this approach were discussed
Π‘ΠΏΠ΅ΠΊΡΡΠ°Π»ΡΠ½ΠΎΠ΅ ΠΏΡΠΎΡΠ²Π»Π΅Π½ΠΈΠ΅ Π°Π³ΡΠ΅Π³Π°ΡΠΈΠΈ ΠΌΠΎΠ»Π΅ΠΊΡΠ» ΠΎΠΊΡΠ°ΠΊΠ°ΡΠ±ΠΎΠΊΡΠΈΡΡΠ°Π»ΠΎΡΠΈΠ°Π½ΠΈΠ½Π° ΠΈ Π΅Π³ΠΎ ΡΠΈΠ½ΠΊΠΎΠ²ΠΎΠ³ΠΎ ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΠ° Π² Π½Π°Π½ΠΎΠΏΠΎΡΠΈΡΡΠΎΠΉ ΠΌΠ°ΡΡΠΈΡΠ΅ ΡΠΈΠ»ΠΈΠΊΠ°ΡΠ½ΠΎΠ³ΠΎ Π³Π΅Π»Ρ
ΠΠ·ΡΡΠ΅Π½Ρ Π»ΡΠΌΠΈΠ½Π΅ΡΡΠ΅Π½ΡΠ½ΠΎ-ΡΠΏΠ΅ΠΊΡΡΠ°Π»ΡΠ½ΡΠ΅ ΡΠ²ΠΎΠΉΡΡΠ²Π° ΠΌΠΎΠ»Π΅ΠΊΡΠ» 2,3,9,10,16,17,23,24-ΠΎΠΊΡΠ°ΠΊΠ°ΡΠ±ΠΎΠΊΡΠΈΡΡΠ°Π»ΠΎΡΠΈΠ°Π½ΠΈΠ½Π° ΠΈ Π΅Π³ΠΎ ΡΠΈΠ½ΠΊΠΎΠ²ΠΎΠ³ΠΎ ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΠ°, Π²Π½Π΅Π΄ΡΠ΅Π½Π½ΡΡ
Π² Π½Π°Π½ΠΎΠΏΠΎΡΠΈΡΡΡΠ΅ ΡΠΈΠ»ΠΈΠΊΠ°ΡΠ½ΠΎ-Π³Π΅Π»Π΅Π²ΡΠ΅ ΠΌΠ°ΡΡΠΈΡΡ. Π£ΡΡΠ°Π½ΠΎΠ²Π»Π΅Π½ΠΎ, ΡΡΠΎ Π-Π°Π³ΡΠ΅Π³Π°ΡΡ ΡΡΠ°Π»ΠΎΡΠΈΠ°Π½ΠΈΠ½ΠΎΠ² ΠΎΠ±ΡΠ°Π·ΡΡΡΡΡ Π½Π° Π½Π°ΡΠ°Π»ΡΠ½ΠΎΠΌ ΡΡΠ°ΠΏΠ΅ ΡΠΎΡΠΌΠΈΡΠΎΠ²Π°Π½ΠΈΡ ΡΠΈΠ»ΠΈΠΊΠ°ΡΠ½ΠΎΠ³ΠΎ ΠΊΠ°ΡΠΊΠ°ΡΠ°. ΠΠ±Π½Π°ΡΡΠΆΠ΅Π½ΠΎ, ΡΡΠΎ ΠΌΠΎΠ½ΠΎΠΌΠ΅ΡΠ½Π°Ρ ΡΠΎΡΠΌΠ° ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΠ° ΡΠΈΠ½ΠΊΠ° Π² ΠΌΠ°ΡΡΠΈΡΠ΅ Π³Π΅Π»Ρ Π²ΠΎΡΡΡΠ°Π½Π°Π²Π»ΠΈΠ²Π°Π΅ΡΡΡ ΠΏΡΠΈ Π²ΡΡΡΡ
Π°Π½ΠΈΠΈ ΡΠΈΠ»ΠΈΠΊΠ°ΡΠ½ΠΎΠ³ΠΎ ΠΌΠ°ΡΠ΅ΡΠΈΠ°Π»Π°. ΠΠ±ΡΡΠΆΠ΄Π°ΡΡΡΡ ΠΏΡΠΈΡΠΈΠ½Ρ ΡΠ°Π·ΡΡΡΠ΅Π½ΠΈΡ Π°Π³ΡΠ΅Π³Π°ΡΠΎΠ² Π² ΠΎΠ³ΡΠ°Π½ΠΈΡΠ΅Π½Π½ΠΎΠΌ ΠΎΠ±ΡΠ΅ΠΌΠ΅ ΠΌΠ°ΡΡΠΈΡΡ Π½Π°Π½ΠΎΡΠ°Π·ΠΌΠ΅ΡΠ½ΡΡ
ΠΏΠΎΡ. The luminescent-spectral properties of molecules of 2,3,9,10,16,17,23,24-octacarboxyphthalocyanine and its zinc complex embedded in nanoporous silicate gel matrices were studied. It was found that H-aggregates of the phthalocyanines are formed at the initial stage of formation of the silicate framework. It was discovered that the monomeric form of the zinc complex in the gel matrix is restored when the silicate material is dried. The reasons for destruction of the aggregates in the restricted volume of the matrix of nanoscale pores are discussed