Effect of counterions on photoprocesses of thiacarbocyanine in a binary solvent blend

Odinokov, A. V.; Bazilevskii, M. V.; Petrov, N. Kh.; Чибисов, А. К.; Алфимов, М. В.

doi:10.1134/s0018143910050048

High Energy Chem

2010

DOI: 10.1134/s0018143910050048

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Effect of counterions on photoprocesses of thiacarbocyanine in a binary solvent blend

A. V. Odinokov

M. V. Bazilevskii

N. Kh. Petrov

et al.

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Cited by 4 publications

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“…The presence of heavy atoms in the anion even at low concentrations can enhance intersystem crossing if the cation and anion are in close proximity (as a contact pair). Thus, it was found [29,30] that the yield of molecules into the triplet state was greater for PDs with Ianion in a slightly polar solvent.…”

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Concentration Increase of the Singlet-Oxygen Generation Quantum Yield by an Indotricarbocyanine Dye

et al. 2014

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Regularities in the generation of singlet oxygen sensitized by the indotricarbocyanine dye HITC with Iand ClO 4 anions in highly and slightly polar solvents were studied as functions of dye concentration (C d ). The yield of singletoxygen formation (γ Δ ) by HITC (I -) increased in slightly polar solvents as its concentration increased. It was shown that HITC with C d < 10 -7 M in CHCl 3 and <5•10 -6 M in o-dichlorobenzene with any anion was found primarily in the form of free ions. It was established that the concentration increase of singlet-oxygen generation by HITC (I -) was due to the heavy-atom effect of the anion as a result of their existence as contact ion pairs and an increase of the fraction of such pairs in a solution with an increased photosensitizer concentration. The quantum yield of singletoxygen formation for HITC with ClO 4 counterion was stable in various solvents as C d was varied over a wide range.

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Concentration Increase of the Singlet-Oxygen Generation Quantum Yield by an Indotricarbocyanine Dye

et al. 2014

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Association constants and distribution functions for ion pairs in binary solvent mixtures: Application to a cyanine dye system

Odinokov

Basilevsky

Nikitina

2011

The Journal of Chemical Physics

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The computations of the association constants K(ass) were performed at the microscopic level for the ion pair Cy(+)I(-) composed of the complex cyanine dye cation Cy(+) coupled to the negative iodine counterion. The wide array of K(ass) values is arranged by a variation of the composition of the binary solvent mixtures toluene/dimethylsulfoxide with the accompanying change of the solvent polarity. The potentials of mean force (PMFs) are calculated for a set of interionic separations R in the Cy(+)I(-) by a methodology which combines the quantum-chemical techniques for the treatment of the electronic structure of the Cy(+)I(-) system with the recent dielectric continuum approach which accounts for the solvation effects. For a given solute/solvent system the probability function P(R), which describes the distribution of interionic separations, is constructed in terms of the PMFs and implemented for the evaluation of the K(ass).

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Decay kinetics of the excited S1 state of the cyanine dye Cy+I− (thiacarbocyanine iodide): The computation of quantum yields for different pathways

Odinokov

Basilevsky

Petrov

2011

The Journal of Chemical Physics

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This work explains the unordinary solvent effect which was observed in the photochemical decay kinetics for the cyanine dye thiacarbocyanine iodide (Cy(+)I(-)) in binary solvent mixtures toluene/dimethylsulfoxide. The interpretation is formulated in terms of the probability density F(R) describing the distribution of interionic distances R in the ion pair Cy(+)I(-) and depending on the solvent composition. The proper normalization of this distribution is expressed via the degree of association α for the ion pair in a given solvent mixture. The α values are, in turn, extracted by means of the mass action law from the ionic association constants computed in a separate publication. The detailed kinetic scheme includes the empirical parametrization of the R-dependent kinetic constants for different decay channels. The multiparameter fitting procedure represents, with the reasonable parameter values, the dependence of the observed quantum yields on the solvent composition.

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Effect of counterions on photoprocesses of thiacarbocyanine in a binary solvent blend

Cited by 4 publications

References 15 publications

Concentration Increase of the Singlet-Oxygen Generation Quantum Yield by an Indotricarbocyanine Dye

Concentration Increase of the Singlet-Oxygen Generation Quantum Yield by an Indotricarbocyanine Dye

Association constants and distribution functions for ion pairs in binary solvent mixtures: Application to a cyanine dye system

Decay kinetics of the excited S1 state of the cyanine dye Cy+I− (thiacarbocyanine iodide): The computation of quantum yields for different pathways

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