Photoreduction of iron(III) tetraphenylporphyrin in ethanol studied by laser flash photolysis: effects of concentration on quantum yields

1992 ◽  
Vol 88 (3) ◽  
pp. 405 ◽  
Author(s):  
Mikio Hoshino ◽  
Koichi Ueda ◽  
Makoto Takahashi ◽  
Minoru Yamaji ◽  
Yoshimasa Hama
Keyword(s):  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Laser Flash ◽  
Quantum Yields

Laser flash photolysis studies of the formation and reactivities of phenyl(naphthyl)methyl carbocations generated from phosphonium salt precursors

1992 ◽  
Vol 70 (6) ◽  
pp. 1784-1794 ◽  
Author(s):  
E. O. Alonso ◽  
L. J. Johnston ◽  
J. C. Scaiano ◽  
V. G. Toscano
Keyword(s):  
Rate Constants ◽  
Phosphonium Salt ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Ion Pairs ◽  
Laser Flash ◽  
Product Formation ◽  
Quantum Yields ◽  
Back Reaction ◽  
Transient Experiments

The photolysis of several substituted phenyl(naphthyl)methyl triphenylphosphonium chlorides has been examined using a combination of laser flash photolysis experiments and product studies. Both carbocation and radical intermediates have been characterized in the transient experiments, with the relative yields depending strongly on the solvent. For example, in alcohols, acetonitrile, or aqueous solvents cation formation predominates while acetonitrile/dioxane mixtures (5–10%) are required for the observation of radicals. Quantum yields for cation formation vary from 0.79 in methanol to 0.093 in 1:4 acetonitrile/dioxane, as measured by product studies and transient experiments, respectively. The addition of perchlorate salts leads to dramatic enhancements in the cation lifetimes; the effects are particularly pronounced for acetonitrile/dioxane mixtures where the cation yields also increase by factors of 3–4. In this case the effects are attributed primarily to replacement of chloride by perchlorate in the initial ion pairs. The combined data from both solvent and perchlorate salt effects on the cation lifetimes and yields suggest that the excited state of the phosphonium salt cleaves homolytically, followed by electron transfer within the initial radical/triphenylphosphine radical cation pair to generate carbocation, as opposed to direct heterolytic cleavage. The cation yields also indicate that back reaction to regenerate starting material, as well as product formation within the initial geminate cage, occur in some solvents. The effects of solvent and added perchlorate salts on the rate constants for reaction with nucleophiles have been examined. For example, rate constants that vary by an order of magnitude have been measured for quenching by azide ion in various aqueous acetonitrile and trifluoroethanol mixtures.

Properties of singlet- and triplet-excited states of hemicyanine dyes

2014 ◽  
Vol 68 (8) ◽  
Author(s):  
Daniel Mártire ◽  
Walter Massad ◽  
Hernán Montejano ◽  
Mónica Gonzalez ◽  
Paula Caregnato ◽  
...  
Keyword(s):  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Fluorescence Emission ◽  
Emission Spectra ◽  
Laser Flash ◽  
Quantum Yields ◽  
Triplet States ◽  
Fluorescence Emission Spectra ◽  
Fluorescence Quantum Yields ◽  
Hemicyanine Dyes

AbstractThe fluorescence emission spectra and fluorescence quantum yields of hemicyanine dyes LDS 698, LDS 722, and LDS 730 were measured in different media. No transient species was detected in the laser flash-photolysis experiments performed with Ar-saturated solutions of the dyes in methanol. However, in the presence of 0.08 M potassium iodide, the absorption of the triplet states was clearly observed. Oxygen consumption measurements in the absence and presence of a chemical trap (furfuryl alcohol) in MeOH: H2O (φ r = 1: 1) solutions of the dyes containing KI confirmed the generation of singlet molecular oxygen.

Time-resolved nanosecond and picosecond absorption studies of excited-state properties of 1-thiobenzoylnaphthalene

1989 ◽  
Vol 67 (6) ◽  
pp. 967-972 ◽  
Author(s):  
R. Minto ◽  
A. Samanta ◽  
P.K. Das
Keyword(s):  
Rate Constants ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Picosecond Laser ◽  
Laser Flash ◽  
Quantum Yields ◽  
Pulse Excitation ◽  
Nanosecond Laser Pulse ◽  
Nanosecond Laser ◽  
Quenching Rate

1-Thiobenzoylnaphthalene (TBN), known for its pericyclization reaction from the lowest excited singlet state (S1), has been subjected to nanosecond and picosecond laser flash photolysis studies. The two major transients observed in the course of nanosecond laser pulse excitation are (i) the short-lived triplet characterized by two absorption maxima (400–410 and 740–750 nm) and submicrosecond intrinsic lifetimes (80–130 ns) and (ii) a relatively long-lived species (λmax = 520 nm and τ = 220–240 ns). Various triplet-related photophysical data of TBN, including self-quenching and bimolecular quenching rate constants, have been determined. The existence of a photochemical path from S1 manifests itself in low intersystem crossing quantum yields, particularly in the polar/hydrogen-bonding solvent, methanol. From the build-up of the triplet under picosecond excitation into S1 the lifetime of the latter is estimated to be ≤ 50 ps (in benzene). The fast intrinsic decay of TBN triplet is attributable to facile intra- and intermolecular photochemistry. The 520 nm transient species could not be definitively assigned, except that it is neither a triplet nor a triplet-derived product and that it arises via photochemistry from S1. Keywords: laser flash photolysis, triplet, transients, absorption maxima, lifetimes, quenching rate constants, photochemistry, 1-thiobenzoylnaphthalenes.

Singlet Mechanism for Trans → Cis Photoisomerization of Quaternary Salts of 4-Substituted 4′-Azastilbenes (R = CN, H, CH3, and OCH3) and their Quinolinium Analogues. VIII

1985 ◽  
Vol 40 (5) ◽  
pp. 525-537 ◽  
Author(s):  
H. Görner ◽  
A. Fojtik ◽  
J. Wróblewski ◽  
L. J. Currell
Keyword(s):  
Triplet State ◽  
Low Temperatures ◽  
Room Temperature ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Ion Pairs ◽  
Laser Flash ◽  
Quantum Yields ◽  
Polar Solvents ◽  
Effects Of Temperature

The trans → cis photoisomerization of a series of substituted stilbazolium salts (At+X− , At+: trans-1-alkyl-4-[4-R-styryl]-pyridinium and -quinolinium, R = CN. H, CH3 and OCH3, X− = I and ClO4−) was studied by laser flash photolysis and steady state irradiation measurements. The quantum yields of cis ⇄ trans photoisomerization (ϕc → t and ϕt → c ) and of fluorescence of the trans isomers (ϕf) were determined in several solvents at room temperature and at low temperatures in mixtures of either 2-methyltetrahydrofuran-dichloromethane or ethanolmethanol (E-M). In polar solvents at room temperature ϕt → c is substantial ( ≧ 0.3) and ϕf is small (10−3-10−2). Competition of fluorescence and an activated step in the trans → cis pathway is indicated by the effects of temperature on ϕf and ϕt → c (activation energy: 2 - 3 kcal/mol). A transient, observed only at low temperatures (lifetime τT > 0.5 ms in E-M below -170°C), is assigned to the lowest triplet state with trans configuration. On the basis of the effects of temperature on ϕf, ϕt → c , and the triplet yield and those of quenchers on ϕf and ϕt → c , involvement of the triplet state in the twisting process at room temperature is excluded. Therefore, a singlet mechanism is suggested for the trans → cis photoisomerization of the stilbazolium salts examined. Significant reduction of ϕt → c for iodides in solvents of moderate polarity, where ion pairs are present, is accounted for by photoinduced electron transfer in competition to trans → cis photoisomerization.

Photochemistry of α-chloro- and α-bromoacetophenone. Determination of extinction coefficients for halogen–benzene complexes

1988 ◽  
Vol 66 (6) ◽  
pp. 1474-1478 ◽  
Author(s):  
W. G. McGimpsey ◽  
J. C. Scaiano
Keyword(s):  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Benzene Solution ◽  
Halogen Bond ◽  
Bond Cleavage ◽  
Laser Flash ◽  
Quantum Yields ◽  
Extinction Coefficients ◽  
Transient Data

The photochemical dehalogenation of α-haloacetophenones (Cl, Br) in benzene solution has been examined under conditions of continuous and pulsed laser irradiation. Product and quantum yield studies indicate that carbon-halogen bond cleavage occurs with quantum yields of 0.88 and 0.41 for α-chloro- and α-bromoacetophenone, respectively. These values are based on trapping studies in which the PhC(O)ĊH2 radicals produced photochemically are scavenged by hydrogen donors such as benzenethiol. Laser flash photolysis studies lead to intense transient signals due to benzene–halogen complexes. Combination of transient data and quantum yields lead to extinction coefficients of 1 800 and 23 700 M−1 cm−1 for the chlorine (490 nm) and bromine (550 nm) complexes, respectively.

Competing photodehydration and excited-state intramolecular proton transfer (ESIPT) in adamantyl derivatives of 2-phenylphenols

2011 ◽  
Vol 89 (2) ◽  
pp. 221-234 ◽  
Author(s):  
Nikola Basarić ◽  
Nikola Cindro ◽  
Yunyan Hou ◽  
Ivana Žabčić ◽  
Kata Mlinarić-Majerski ◽  
...  
Keyword(s):  
Excited State ◽  
Carbon Atom ◽  
Proton Transfer ◽  
Phenyl Ring ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Laser Flash ◽  
Intramolecular Proton Transfer ◽  
Hydroxyl Group ◽  
Quantum Yields

2-Phenylphenol derivatives strategically substituted with a hydroxyadamantyl substituent were synthesized and their photochemical reactivity was investigated. Derivatives 9 and 10 undergo competitive excited-state intramolecular proton transfer (ESIPT) from the phenol to the carbon atom of the adjacent phenyl ring and formal ESPT from the phenol to the hydroxyl group coupled with dehydration. These two processes (both via S1) give rise to two classes of quinone methides (QMs) that revert to starting material or react with nucleophiles, respectively. ESIPT to carbon atoms was studied by performing photolyses in the presence of D2O, whereupon deuterium incorporation to the adjacent phenyl ring was observed ([Formula: see text] = 0.1–0.2). The competing formal ESPT and dehydration takes place with quantum yields that are an order of magnitude lower and was studied by isolation of photomethanolysis products. Derivative 8 did not undergo ESIPT to carbon atom. Owing to the presence of an intramolecular H bond, an efficient ESIPT from the phenol to the hydroxyl group coupled with dehydration gives a QM that efficiently undergoes electrocyclization (overall [Formula: see text] = 0.33), to give chroman 16. In addition, spiro[adamantane-2,9′-(4′-hydroxy)fluorene] (12) undergoes ESIPT, unlike the previously reported unreactive parent 2-hydroxyfluorene. The reactive singlet excited states of the prepared biphenyl and fluorene molecules were characterized by fluorescence spectroscopy, whereas laser flash photolysis (LFP) was performed to characterize the longer lived QM intermediates.

Photochemistry of alkyl esters of benzoylformic acid

1984 ◽  
Vol 62 (2) ◽  
pp. 386-391 ◽  
Author(s):  
M. V. Encinas ◽  
E. A. Lissi ◽  
A. Zanocco ◽  
L. C. Stewart ◽  
J. C. Scaiano
Keyword(s):  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Laser Flash ◽  
Quantum Yields ◽  
Type Ii ◽  
Alkyl Esters ◽  
Hydrogen Atoms ◽  
Isopropyl Esters ◽  
Norrish Type ◽  
Competing Reactions

The photodecomposition of several alkylbenzoylformates has been examined using quantum yield and laser flash photolysis techniques. The Norrish Type II reaction is a major triplet deactivation path in all substrates having γ-hydrogen atoms. Representative triplet lifetimes are 670, 500, and 310 ns, for the methyl, ethyl, and isopropyl esters, respectively, in 1:4 chlorobenzene: n-heptane at 298 K. Product studies suggest that several competing reactions are involved in the decay of the 1,4-biradical; some of these lead to highly absorbing (and presumably quenching) products, that make it essential to extrapolate quantum yields to "zero conversion" conditions.

scholarly journals Decomposition of S-Nitrosothiols Induced by UV and Sunlight

2009 ◽  
Vol 2009 ◽  
pp. 1-5 ◽  
Author(s):  
Manoj M. Veleeparampil ◽  
Usha K. Aravind ◽  
C. T. Aravindakumar
Keyword(s):  
Photodynamic Therapy ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Laser Flash ◽  
Major Product ◽  
Quantum Yields ◽  
Induced Decomposition ◽  
Derivatives Of ◽  
Oxidation Of No ◽  
Hplc Analyses

Photochemical release of nitric oxide (NO) from the S-nitroso derivatives of glutathione, L-cysteine, N-acetyl-L-cysteine, L-cysteinemethylester, D,L-penicillamine, N-acetyl-D,L-penicillamine, and N-acetylcysteamine has been investigated at neutral and acidic pH. The release of NO from RSNO is one of the key reactions that could be utilized in photodynamic therapy. The UV-VIS and HPLC analyses have shown that under argon saturated conditions, disulfide (RSSR) is the major product of UV as well as sunlight induced decomposition. While in aerated conditions, nitirite—the end product of the oxidation of NO—was also observed along with disulfide. The formation of thiyl radical as the intermediate was reconfirmed by laser flash photolysis. The initial rate of formation of NO was on the order of 10−10dm3mol−1s−1. The quantum yields of these reactions were in the range of 0.2–0.8. The high quantum yields observed in the photo induced release of NO from RSNO using both UV and sunlight demonstrate the potential application of these reactions in photodynamic therapy.

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