Limitation of high-power optical radiation by organic molecules: I. Substituted pyranes and cyanine dyes

Kopylova, T. N.; Svetlichnyi, V. A.; Mayer, G. V.; Резниченко, А. В.; Подгаецкий, В. М.; Пономарева, О. В.; Samsonova, L. G.; Filinov, D N; Pomogaev, Vladimir A.; Tel’minov, E. N.; Лапин, И. Н.; Svetlichnaya, N N; Sinchenko, Elena

doi:10.1070/qe2003v033n11abeh002532

Cited by 17 publications

(9 citation statements)

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“…The parameters developed and tested on benzene derivatives are especially focused to obtain the most reliable excited electronic energy level diagrams of organic cyclic and heterocyclic molecules and compounds 20, 21. The obtained results were in good agreement with experiment 22, 23. The INDO/sp approach is applied due to high efficiency among others for organic photonics, but it can be replaced easily by other more effective and cheap techniques.…”

Section: Introductionsupporting

confidence: 88%

Elongation method for calculating excited states of aromatic molecules embedded in polymers

Pomogaev

Pomogaeva

et al. 2009

Int J of Quantum Chemistry

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Photophysical properties of polyethylene structures embedding aromatic fragments (benzene, anthracene, 4-dicyanomethylene-4H-pyran, tryptophan, and estradiol) responsible for existence lowest electronically excited states were studied by new technique involving the elongation method applied to quantum-chemical calculations. Absorption spectra and some photophysical properties were obtained. The comparison between the elongation and the conventional calculations was made, and it is shown that the elongation method is a powerful tool to determine the excited states as well as optical properties for large systems.

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Section: Introductionsupporting

confidence: 88%

Elongation method for calculating excited states of aromatic molecules embedded in polymers

Pomogaev

Pomogaeva

et al. 2009

Int J of Quantum Chemistry

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“…The appearance of the LOR effect in this situation is additional evidence that the principal limitation mechanism is induced triplet-triplet absorption, which does not contradict the literature [5,25] on LOR for Pc and Nc dyes.…”

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confidence: 49%

“…The experimental apparatus for investigating LOR using the transmission T W of activated metal complexes with 1,2-Nc xerogels as functions of the power of incident laser radiation W has been described in detail [5,25]. The radiation source was the second harmonic of a Nd:YAG laser (λ las = 532 nm, E pul ≤ 70 mJ, τ pul = 15 ns).…”

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confidence: 99%

Spectral and nonlinear optical properties of metal complexes with 1,2-naphthalocyanine in silicate gel matrices

et al. 2007

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UDC 535.37We have studied the influence of the method for embedding metal (Yb or Zn) complexes with 1,2-naphthalocyanine into nanoporous silicate xerogels (directly during sol-gel synthesis or by impregnation of the xerogel) and the nature of the Yb 3+ exoligand (anionic Cl -or acetylacetone) on the spectral properties and structure of impurity molecular centers. It is shown that the degree of protonation and/or aggregation of the studied metal complexes is determined by the average surface concentration of HO-Si* silanol groups of the gel-matrix nanopores. It is established that the Yb complex with 1,2-naphthalocyanine and the anionic ligand Clpenetrates to the greatest extent from solution into the inner cavities of the xerogel (degree of impregnation). This is due to quasichemical interaction of pigment molecules with the dehydroxylated nanopore surface containing *Si-O-Si* siloxane bridges. It is shown that the investigated metal complexes in both liquid solutions and solid-state silicate gel-matrices have a limiting effect on powerful optical radiation.Key words: sol-gel synthesis, silicate xerogel, metal complex of 1,2-naphthalocyanine, exoligand, cationic forms, aggregates, limitation of optical radiation.Introduction. Nonlinear limitation of optical (laser) radiation (LOR) that is manifested as a decrease in the transmission coefficient of a sample illuminated at high flux intensity or density may be based on physical mechanisms of differing nature. The best results for LOR using organic dyes were achieved in materials containing macrocyclic tetrapyrrole compounds (porphyrins or phthalocyanines) [1][2][3][4][5]. The principal LOR mechanism in this instance is related to the generation of reflected (or reverse) saturable absorption (RSA), i.e., absorption from excited singlet or triplet states. The increased probability of intercombinational conversion of phthalocyanine complexes with such heavy metals as In, Sn, Pb, etc. (heavy-atom internal effect) enhances the appearance of induced absorption in the triplet levels through the action of nanosecond laser radiation [6][7][8][9][10][11]. Because the effective absorption cross section from T 1 -states is much greater than that for S 0 -states in the spectral "transparency window" (450-600 nm) of metallophthalocyanines (MPc) [6,12], the best results for LOR are obtained at λ = 532 nm for these MPc. The broad capabilities of tetrapyrrole macrocyclic compounds for structural modifications through addition of peripheral substituents and expansion of the conjugated system (for example, by annelating benzene rings) and the presence of exoligands with various chemical structures on the metal complexes can have a substantial influence on the position of the absorption bands from the ground state (to regulate the spectral transmission range) of the material used for LOR. LOR by porphyrins and phthalocyanines with various peripheral substituents and central metal ions (with or without anionic and organic ligands) and linearly annelated benzene rings [2,3-naphthalocyan...

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“…Recently, we have shown [8] that substituted DCMs attenuate the emission of the Nd-YAG laser second harmonics, but their attenuation coefficient ranks below that of fullerenes and polymethine or phthalocyanine dyes.…”

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confidence: 98%

Theoretic and Experimental Study of Photoprocesses in Substituted 4-Dicyanomethylene-4H-pyrans

et al. 2005

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1 Substituted 4-dicyanomethylene-4H-pyran (DCM) derivatives are widely used in quantum electronics and optoelectronics as active media of tunable lasers, emitting layers of organic light diodes [1,2], and nonlinearoptics media [3][4][5]. The active media based on substituted DCMs lase in the red spectral region in solutions and solid matrices [6,7], have high photochemical stability, and exhibit a broad emission band up to 120 nm. Their absorption and emission spectra practically do not overlap (the Stocks shift attains 160 nm). This makes it possible to obtain the high efficiency of emission conversion in both the transverse and longitudinal modes of excitation. Reabsorption losses are low even at high concentrations of active molecules.Some DCMs possess nonlinear optical properties. Recently, we have shown [8] that substituted DCMs attenuate the emission of the Nd-YAG laser second harmonics, but their attenuation coefficient ranks below that of fullerenes and polymethine or phthalocyanine dyes.The aim of this work was to study the photoprocesses occurring in the molecules of substituted DCMs and to reveal the effect of the molecular structure on their spectral and luminescent parameters. EXPERIMENTALThe structural formulas of the 4-dicyanomethylene-4H-pyrans under study are given below.The quantum-chemical study of photoprocesses occurring in these molecules was performed by the INDO/S method with the use of an original software package [9]. The use of this method allows us to build the complete scheme of electronically excited states of molecules, to calculate their dipole moment, oscillator strength, charge distribution in molecules, and the spec-1 e-mail:svet@elefot.tsu.ru tra of induced absorption from excited triplet and singlet states. The use of the theory of nonradiative transfer of the energy of electronic excitation in a molecule makes it possible to estimate the rate constants of deactivation processes [10], to establish their trends depending on the molecular structure, and to predict the molecular structures with given properties.The experimental studies of the photoprocesses in DCM were carried out with the use of a Specord M40 spectrophotometer and a Hitachi 85 spectrofluorimeter. The fluorescence quantum yield of the molecules was determined relative to Rhodamine C in ethanol ( γ = 0.65) according to the procedure described in [11].Ethyl acetate, ethanol, and dimethyl sulfoxide (DMSO) were used as solvents. Their purity was controlled by spectrophotometry. The concentration of the molecules under study was 10 -4 (in recording absorption spectra) and 10 -6 -10 -5 mol l -1 (in recording the spectra and measuring the quantum yields of fluorescence).Substituted DCMs under study were synthesized by Ponomareva O.V. (Dolgoprudnyi, NPF DELTAKOR) and were used without additional purification. RESULTS AND DISCUSSIONExperimental and calculated positions of the absorption band maximums of substituted DCM under study are listed in Table 1. Note that the experimental data agree well with the results obtained ...

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Limitation of high-power optical radiation by organic molecules: I. Substituted pyranes and cyanine dyes

Cited by 17 publications

References 1 publication

Elongation method for calculating excited states of aromatic molecules embedded in polymers

Elongation method for calculating excited states of aromatic molecules embedded in polymers

Spectral and nonlinear optical properties of metal complexes with 1,2-naphthalocyanine in silicate gel matrices

Theoretic and Experimental Study of Photoprocesses in Substituted 4-Dicyanomethylene-4H-pyrans

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