Photoinduced electron transfer in solutions of A Pd-porphyrin-quinone complex

Photoinduced electron transfer (PET) in a Pd-porphyrin-quinone complex (Pd-P-Q) was investigated using the flash photolysis method in microsecond and picosecond range and by luminescence. The investigations were performed for toluene solutions. Intramolecular PETs in the lower excited singlet state (k_CT=1.7·10¹⁰ sec⁻¹) and in the triplet state (k_CT=2.5·10⁸sec⁻¹) were observed. For a quantum yield of the triplet state that is close to 1 in Pd-porphyrin (Pd-P) this yield is equal to 0.4 in Pd-P-Q. This decrease is the result of PET in the excited state and, possibly, in an unrelaxed triplet state. Triplet Pd-P-Q molecules were efficiently quenched by unexcited molecules, and this process is related to intermolecular charge transfer. This electron transfer is likely to occur from the Pd-P protion of an excited molecule to the quinone protion of an unexcited molecule in the collisional complex (Pd-P-Q)₂. Charged radicals, formed once the collisional complex is transferred and separated, have a wide absorption band with a maximum of about 960 nm. The average lifetime of the radicals was about 2 msec. Institute of Molecular and Atomic Physics, Academy of Sciences of Belarus, 70, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No 1 pp. 61–70, January–February, 1997.     

Vectorial photoinduced electron transfer in phospholipid vesicles and LB bilayers

Summary Photoinduced electron transfer (PET) was studied in phospholipid vesicles and in Langmuir-Blodgett bilayers in the attempt to produce a model for electron transfer processes in biological media. Spatial organization of the reaction centers in lipid membranes needs to be controlled in order to provide high efficiency of light-to-chemical energy conversion. We designed a phospholipid system where the donor is localized in the inner bilayer whereas the acceptor is at the polar groups-water interface. We used dipalmitoylphosphatidic acid vesicles containing low molar fractions of dipalmitoylphosphatidylcholine with pyrene (donor) bound to one of the alkyl chains. Methylviologen (acceptor) was added to the external aqueous phase; upon photoexcitation of the donor we observed the electron transfer to take place in a unidirectional manner from the inside of the bilayer to the interface. Information about the location of the donor was obtained studying the photophysical properties of the pyrene chromophore in vesicles and in LB layers. The photoinduced electron transfer reaction was evidenced by quenching of pyrene fluorescence in the presence of increasing concentrations of acceptor, the process was studied both with steady-state and time-resolved fluorescence emission. Fluorescence intensity was found to decrease with increasing concentration of methylviologen, similar results were obtained for vesicles and LB layers of analog composition immersed in a methylviologen solution. Lifetimes of the excited species were found to be of the same order of magnitude in vesicle and LB-layer systems. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Dynamics of photoinduced electron transfer in model multiporphyrin ensembles

It is shown by the methods of picosecond fluorescent and femtosecond absorptive spectroscopy that in the nanosize self-assembled complexes based on a Zn-octaethylporphyrin dimer and electron acceptors of different nature (quinone, anthraquinone, pyromellitimide) deactivation of the energy of electron excitation is caused by the nonradiative S-S-energy transfer (for times ≤10 psec) and photoinduced charge transfer (within the range of 300 fsec-700 psec). In tetrads an electron is transferred from a porphyrin extra-ligand to quinone for distances r_DA≈18–21 Å by the “superexchange” mechanism. In triads, the charge transfer from a dimer to a fluorinated porphyrin extra-ligand is efficient at 120-77 K.     

Intermolecular photoinduced electron-transfer processes between C60 and aniline derivatives in benzonitrile

The quenching behavior of the triplets of C₆₀ by various aniline derivatives (1a-d and 2a-e) was investigated by means of laser flash photolysis in benzonitrile at 293 K. Electron transfer process was proposed to be the main mechanism because of the direct detection of radical ions of aniline derivatives and C₆₀ in time-resolved transient absorption spectra. The quenching rate constants (k_q) of by different substrates determined at 740 nm approach or reach the diffusion-controlled limit. DFT method was employed to calculate the unknown oxidation potentials of substrates in solution. With these E_ox values, free energy changes (ΔG) were obtained through Rehm-Weller equation. Dependence of observed quenching rate constants on the free energy changes further indicates the photoinduced reactions between ³C₆₀^* and substrates proceed through an electron transfer mechanism. Obtained k_q values for the aniline derivatives are impacted obviously by ground-state configurations and the kinds substituents quantified by Hammett σ constant. Good correlation between log k_q and σ values conforms to the empirical Hammett equation. A more negative ρ value (−3.356) was gained for anilines (2a-e) than that of N,N-dimethylanilines (1a-d) (−1.382), which suggests a more susceptible reactivity for the former substrates. Charge density distribution of reaction center “N” originated from quantum calculation supports this suggestion. In addition, a relationship between quenching rate constants and solvent viscosity was gained from C₆₀/dimethyl-p-toluidine system in altered mixtures of acetonitrile and toluene.     

On the investigation of laser-induced carriers in silicon in the picosecond time range

The dependence of the time behaviour of optically-induced carriers on linear recombination and diffusion is studied taking into account the exciting pulse duration. If the pulse duration becomes comparable to the carrier lifetime in the case of linear recombination the exciting pulse influences the temporal behaviour of the carriers significantly. If the temporal behaviour of the carriers is to be determined by diffusion an exciting pulse, short with respect to a characteristic diffusion time, strongly influences this behaviour. These calculations were used to fit some experimental results of time-resolved reflectivity measurements of silicon.

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Zusammenfassung Es wird das zeitliche Verhalten von optisch angeregten Ladungsträgern bei linearer Rekombination und Diffusion unter Berücksichtigung der Anregungsimpulslänge untersucht. Während die Anregungsimpulslänge im Fall der linearen Rekombination erst einen merklichen Einfluß auf das Zeitverhalten der Ladungsträger gewinnt, wenn sie in die Größe der Rekombinationszeit gelangt, wird ihr Einfluß auf das Diffusionsverhalten bemerkbar, wenn sie klein gegen die Diffusionszeit ist. Die numerischen Rechnungen wurden zur Interpretation von zeitaufgelösten Reflexionsmessungen an Silizium angewandt.

     

Luminescent analysis of photoinduced detoxification of phenol in the presence of humic substances

We have studied the effect of two detoxifying factors on aqueous solutions of phenol: UV radiation from different sources, and humic substances. The phenol photoconversion processes were monitored by the fluorescent method; the toxicity of the phenol solutions was monitored using a bioluminescence test. It was shown that effective detoxification of an aqueous phenol solution occurs as a result of addition of humic substances; the most effective photoinduced detoxification was detected when using UV radiation from an exciplex lamp (λ_rad = 308 nm). Other UV irradiation sources and the combined action of UV irradiation and humic substances are characterized by a smaller detoxifying effect. In this case, irradiation using an exciplex lamp (λ_rad = 222 nm) increases the toxicity of the phenol solution both in the presence and in the absence of humic substances. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 6, pp. 741–745, November–December, 2006.     

Combination of LFP‐TRIR spectroscopy and DFT computation as a tool to determine the intermediate during the photooxidation of triarylphosphine

Laser flash photolysis‐time‐resolved infrared spectroscopy (LFP‐TRIR) was performed on an acetonitrile or dichloromethane solution of triarylphosphines, Ar₃P, in air. A transient spectrum consisting of several absorption bands appeared in the region of 1050–1300 cm^?1 on the TRIR on a microsecond timescale, which disappeared on a millisecond timescale. To identify the observed transient intermediate, the IR spectra of possible intermediates of the photoreaction were simulated by theoretical calculations based on density functional theory (DFT). The IR spectrum simulated for the phosphine peroxidic radical cation, Ar₃P⁺OO^?, well predicted the observed IR spectrum, showing that Ar₃P⁺OO^? is formed as a transient intermediate upon the LFP of Ar₃P in air. Copyright © 2014 John Wiley & Sons, Ltd.     

Oxidation of substituted triazines by sulfate radical anion (SO) in aqueous medium: a laser flash photolysis and steady state radiolysis study

Laser flash photolysis has been used to determine the bimolecular rate constants and the spectral nature of the intermediates obtained by the reaction of sulfate radical anion (SO) with 1,3,5‐triazine (T), 2,4,6‐trimethoxy‐1,3,5‐triazine (TMT), 2,4‐dioxohexahydro‐1,3,5‐triazine (DHT), and 6‐chloro N‐ethyl N'‐(1‐methylethyl)‐1,3,5‐triazine‐2,4‐diamine (atrazine, AT). The rate constants determined were in the range 4.6 × 10⁷–3 × 10⁹ dm³ mol^?1 s^?1 at pH 6. The transient absorption spectra obtained from the reaction of SO with T, TMT, DHT and AT has an absorption maximum in the region 320–350 nm and was found to undergo second‐order decay. The intermediate species is assigned to N‐yl C(OH) radical of T (TOH^?), carbon centered neutral radical of TMT, an OH‐adduct of AT and an N‐centered radical in the case of DHT. The interpretations on the experimental results obtained from TMT are supported by DFT calculation using Gaussian 03. Steady state radiolysis technique has also been used to investigate the degradation of AT induced by SO. The degradation profile indicated that about 99% of AT has been decomposed after an absorbed gamma‐radiation dose of 7.5 kGy. The degradation yield of AT (expressed as G(‐AT)) was found to be 0.26 µ mol J^?1. The degradation reactions initiated by SO may thus be employed as a potential alternative for ^?OH‐induced degradation of triazines. Copyright © 2007 John Wiley & Sons, Ltd.     

Probing the orientation of porphyrin oligomers in a liquid crystal solvent – a triplet state electron paramagnetic resonance study

ABSTRACT

Linear porphyrin oligomers have found various applications as synthetic molecular wires in the context of light harvesting, solar energy conversion and molecular electronics. In many of these applications a partial ordering of the molecules helps to improve the reaction efficiency or device performance. In this work we study the orientational properties of the building blocks of such porphyrin-based molecular wires, namely a porphyrin monomer and the corresponding butadiyne-bridged dimer. The porphyrins have been embedded in the nematic liquid crystal solvent 4-cyano-4'-pentylbiphenyl (5CB) and the anisotropic properties of their photogenerated triplet states were characterised by transient electron paramagnetic resonance (EPR) spectroscopy. When aligned in strong magnetic fields, the liquid crystal molecules impose their orientational anisotropy onto the solute guest molecules whose orientation-dependent magnetic properties can then be explored. The line shape analysis of the porphyrin triplet state EPR spectra – highly sensitive to small conformational changes – confirms the orientation of the zero-field-splitting (ZFS) tensors previously determined for these molecules by magnetophotoselection experiments. A biaxial distribution function is shown to be necessary to simulate the experimental EPR data. The biaxial behaviour, in conjunction with symmetry considerations, allows an unambiguous assignment of the three ZFS tensor axes to the molecular axes. From the determined orientational distributions of the porphyrins in 5CB, the biaxial order parameters for both molecules were calculated.     

Nature of delayed luminescence of N-methylindole and indole in the gas phase

We have studied the spectral characteristics and the kinetics of delayed (long-lived) luminescence of N-methylindole and indole in the gas phase. For N-methylindole, we observed delayed annihilation fluorescence, spectrally matching fast fluorescence. There is no delayed annihilation fluorescence for indole, but we observed a delayed luminescence band with wavelength at the maximum 535 nm, which we interpreted as luminescence of free radicals formed as a result of dissociation of the N-H bond. We hypothesize that the excited states of the free radicals arise as a result of nonradiative energy transfer from indole in the triplet state to indole free radicals in the doublet state. The lifetimes of the triplet states of N-methylindole and indole in the gas phase at T = 373 K, obtained from analysis of the delayed luminescence kinetics, are 2.5 msec and 1.0 msec. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 3, pp. 341–345, May–June, 2007.     

Structural requirements for efficient photoinduced electron transfer (PET) quenching in 9-aminoalkylanthracenes

The structure-quenching relationship in 9-aminoalkylanthracenes is examined by the synthesis and fluorescence evaluation of five derivatives; it is observed that benzylic 2° and 3° amines lead to 95% quenching of anthracene fluorescence in water, while other amines afford substantially lower quenching efficiencies.     

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.     

Josephson current versus potential strength of the interface in ferromagnetic superconductors

Based on the scattering theory, we calculate the Josephson current in a junction between two ferromagnetic superconductors as a function of the interface potential z. We consider the ferromagnetic superconductor(FS) in three different Cooper pairing states: spin singlet s-wave pairing(SWP) state, spin triplet opposite spin pairing(OSP) state, and spin triplet equal spin pairing(ESP) state. We find that the critical Josephson current as a function of z shows clear differences among the SWP, OSP, and ESP states. The obtained results can be used as a useful tool for determining the pair symmetry of the ferromagnetic superconductors.     

Determination of the Probability of Intermolecular Energy Transfer of the Triplet State of a Number of Tetrapyrrole Molecules in Liquid Solutions

The quenching of the triplet state of a number of Pd porphyrins and chlorophyll a by other complexes of porphyrins with Pd and Fe in liquid solutions was investigated with the use of pulsed photoexcitation. It is shown that the experimental data are consistent with the results of a kinetic analysis of the mechanism of quenching of the triplet state through the formation of excited complexes of interacting molecules. On the basis of analytical and experimental data, the probability values of intermolecular tripletstate energy transfer have been determined: K _ET = 2·10⁴3·10⁵ sec^–1. A conclusion about the character of the excited complexes has been drawn; in particular, the distance between the molecules in the complexes has been estimated to be 5 .     

电场诱导聚合物分子取向对单线态和三线态激子形成截面的影响

通过对聚乙烯咔唑(PVK) 掺杂三(2-苯基吡啶)铱(Ir(ppy)₃)和4-二氰亚甲基-2-叔丁基-6-(1,1,7,7-四甲基久咯呢定基-9-烯基)-4H-吡喃(DCJTB)，PVK 掺杂DCJTB和PVK掺杂Ir(ppy)₃聚合物在成膜时高压电场作用下分子取向变化对单线态和三线态激子形成截面的研究，发现，随着成膜时电场的增强，单线态激子的形成截面在增加，而三线态激子的形成截面却减小. 关键词： 分子取向 激子形成截面 三线态 单线态     

EPR study on the photoinduced electron transfer in the ternary complex (dithiocarbamato,dithiophosphato)copper(II)

The EPR study on equimolar solutions of Cu(dtc)₂ and Cu(dtp)₂ in aerated acetone, toluene and chloroalkane (CHCl₃ and CCl₄) solutions indicates that Cu(dtc)(dtp) is the only complex species present in solution. The analysis of the EPR spectra recorded after photo-irradiation in aerated acetone solutions enables the characterization of the intermediate paramagnetic species and provides a reasonable explanation.     

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.     

Quenching of the triplet state of tetrapyrrole molecules by Ni-, Ag-, and Fe-porphyrins and formation of excited complexes and photoproducts

Using the method of pulse photolysis, we studied the quenching of the triplet state (TS) of a number of tetrapyrrole molecules by complexes of Ni-, Ag-, and Fe-porphyrins in liquid solutions at a temperature of ∼298 K under the conditions where the kinetics are markedly affected by the triplet-triplet annihilation of the molecules of energy donors. In the analysis of experimental data, derivatives for the time dependences of the optical density of the triplet-triplet absorption were determined. The triple-triplet annihilation process was considered for the case of the formation of excited a triplet-triplet complexes of two molecules in the triplet state. A procedure of determining the rate constant for the quenching of the triplet state by foreign molecules (K_q) under the effect of such triplet-triplet annihilation process is proposed and the values of K_q are obtained. For some donor-quencher pairs it is found that the kinetics of the triplet-state deactivation are affected by the formation of short-lived particles with lifetimes both shorter and longer than the triplet-state lifetimes. The conclusion is drawn that such particles are respectively the excited complexes of interacting molecules or ion radicals formed from such complexes in polar solvents. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 3, pp. 296–300, May–June, 2000.     

Electronic Absorption Spectra of Transient Boron-Sulphur Species in the Gas Phase

The vapour phase flash photolysis of boron triiodide, in the presence of carbon disulphide or carbon oxysulphide, produces two sets of spectral absorption bands centred near 412 and 625 nm, respectively. These are attributed to the previously unreported BS₂ radical. The lower states of the gamma emission band system of BS and the alpha and beta systems of BO are confirmed as the ground electronic states.