Laser Flash Photolysis Generation, Spectra, and Lifetimes of Phenylcarbenium Ions in Trifluoroethanol and Hexafluoroisopropyl Alcohol. On the UV Spectrum of the Benzyl Cation

1991 ◽  
Vol 30 (10) ◽  
pp. 1337-1339 ◽  
Author(s):  
Robert A. McClelland ◽  
Christopher Chan ◽  
Frances Cozens ◽  
Agnieszka Modro ◽  
Steen Steenken
Keyword(s):  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Laser Flash ◽  
Uv Spectrum ◽  
Benzyl Cation

ChemInform Abstract: Laser Flash Photolysis Study of the UV Spectrum and Kinetics of Reactions of HOCH2CH2O2 Radicals.

ChemInform ◽  
2010 ◽  
Vol 22 (42) ◽  
pp. no-no
Author(s):  
T. P. MURRELLS ◽  
M. E. JENKIN ◽  
S. J. SHALLIKER ◽  
G. D. HAYMAN
Keyword(s):  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Laser Flash ◽  
Uv Spectrum ◽  
Kinetics Of

Lifetimes and UV-visible absorption spectra of benzyl, phenethyl, and cumyl carbocations and corresponding vinyl cations. A laser flash photolysis study

1999 ◽  
Vol 77 (12) ◽  
pp. 2069-2082 ◽  
Author(s):  
Frances L Cozens ◽  
V M Kanagasabapathy ◽  
Robert A McClelland ◽  
Steen Steenken
Keyword(s):  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Laser Flash ◽  
Styrene Polymerization ◽  
Aryl Group ◽  
Visible Absorption ◽  
Benzyl Cation ◽  
Vinyl Cation ◽  
Uv Visible ◽  
20 Nm

Benzyl (4-MeO, 4-Me, and 4-methoxy-1-naphthylmethyl), phenethyl (4-Me2N, 4-MeO, 3,4-(MeO)2, 4-Me, 3-Me, 4-F, 3-MeO, 2,6-Me2, parent, and 4-methoxy-1-naphthylethyl) and cumyl (4-Me2N, 4-MeO, 4-Me, parent) cations have been studied by laser flash photolysis (LFP) in 2,2,2-trifluoroethanol (TFE) and 1,1,1,3,3,3-hexafluoroisopropanol (HFIP). In most cases styrene or α-methylstyrene precursors were employed for the phenethyl and cumyl ions, the intermediate being obtained by solvent protonation of the excited state. Benzyl cations were generated by photoheterolysis of trimethylammonium and chloride precursors. While a 4-MeO substituent provides sufficient stabilization to permit observation of cations in TFE, cations with less stabilizing substituents usually require the less nucleophilic HFIP. Even in this solvent, the parent benzyl cation is too short-lived (lifetime <20 ns) to be observed. When generated in HFIP, phenethyl cations can be seen to react with unphotolyzed styrene, giving rise to dimer cations that are observed to grow in as the initial phenethyl cation decays. The dimer cations, in common with the oligomer cations seen in cationic styrene polymerization, have a λmax 15-20 nm higher than the monomer and react with both solvent and styrene several orders of magnitude more slowly. This stabilization relative to the phenethyl may reflect an interaction with the aryl group present at the gamma-carbon. Cations 4-MeOC6H4C+(R)-CH3 (R = Me, Et, i-Pr, t-Bu, cyclopropyl, C6H5, 4-MeOC6H4) were generated in TFE via the photoprotonation route. The alkyl series shows that steric effects are important in the decay reaction. The cation with R = cyclopropyl is a factor of 1.5 less reactive than the cation where R = phenyl. Several vinyl cations have also been generated by photoprotonation of phenylacetylenes. ArC+=CH2 has a reactivity very similar to that of its analog ArC+H-CH3, the vinyl cation being slightly (factors of 2-5) shorter-lived. For the various series of cations, including vinyl, substituents in the aryl ring have a consistent effect on the λmax, a shift to higher wavelength relative to hydrogen of 15 nm for 4-Me, 30 nm for 4-MeO, and 50 nm for 4-Me2N.Key words: photogenerated carbocations, carbocation lifetime, styrene, photoprotonation.

Effect of Aggregation on Bacteriochlorin a Triplet-state Formation: A Laser Flash Photolysis Study¶

2002 ◽  
Vol 76 (5) ◽  
pp. 480 ◽  
Author(s):  
Xavier Damoiseau ◽  
Francis Tfibel ◽  
Maryse Hoebeke ◽  
Marie-Pierre Fontaine-Aupart
Keyword(s):  
Triplet State ◽  
State Formation ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Laser Flash

A Laser Flash Photolysis and Pulse Radiolysis Study of Primary Photochemical Processes of Flumequine¶

2000 ◽  
Vol 72 (4) ◽  
pp. 451 ◽  
Author(s):  
M. Bazin ◽  
F. Bosca ◽  
M. L. Marin ◽  
M. A. Miranda ◽  
L. K. Patterson ◽  
...  
Keyword(s):  
Pulse Radiolysis ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Laser Flash ◽  
Photochemical Processes

Laser Flash Photolysis Studies of the UVA Sunscreen Mexoryl® SX

1999 ◽  
Vol 70 (3) ◽  
pp. 292
Author(s):  
Ann Cantrell ◽  
David J. McGarvey ◽  
Louise Mulroy ◽  
T. George Truscott
Keyword(s):  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Laser Flash

Singlet Methylene Removal Rate Constants from the (0,1,0) Vibrational Level: Enhancement via Complex-Mediated Vibrational Relaxation

2001 ◽  
Vol 215 (6) ◽  
Author(s):  
M.A. Buntine ◽  
G.J. Gutsche ◽  
W.S. Staker ◽  
M.W. Heaven ◽  
K.D. King ◽  
...  
Keyword(s):  
Vibrational Level ◽  
Rate Constants ◽  
Vibrational Relaxation ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Removal Rate ◽  
Laser Flash ◽  
Laser Absorption ◽  
Photolysis Laser ◽  
Singlet Methylene

The technique of laser flash photolysis/laser absorption has been used to obtain absolute removal rate constants for singlet methylene,

Electron transfer sensitized photolysis of 'onium salts

1988 ◽  
Vol 66 (2) ◽  
pp. 319-324 ◽  
Author(s):  
R. J. DeVoe ◽  
M. R. V. Sahyun ◽  
Einhard Schmidt ◽  
N. Serpone ◽  
D. K. Sharma
Keyword(s):  
Electron Transfer ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Laser Flash ◽  
Quantitative Model ◽  
Intersystem Crossing ◽  
Single Electron Transfer ◽  
Onium Salts ◽  
Encounter Complex ◽  
Back Electron Transfer

We have studied the anthracene-sensitized photolyses of both diphenyliodonium and triphenylsulphonium salts in solution using both steady-state and laser flash photolysis techniques. Photoproducts, namely, phenylated anthracenes along with iodobenzene or diphenylsulphide, respectively, are obtained from both salts with quantum efficiencies of ca. 0.1 at 375 nm. We infer the intermediacy of diphenyliodo and triphenylsulphur radicals formed by single electron transfer from the singlet-excited anthracene. We have developed a quantitative model of this chemistry, and identify the principal sources of inefficiency as back electron transfer, which occurs at nearly the theoretically limiting rate, intersystem crossing from the initially formed sensitizer–'onium salt encounter complex, and in-cage radical recombination.

Phototransformations of bridgehead-substituted dibenzobarrelenes. Steady-state and laser flash photolysis studies

1987 ◽  
Vol 52 (25) ◽  
pp. 5512-5517 ◽  
Author(s):  
S. Pratapan ◽  
K. Ashok ◽  
D. R. Cyr ◽  
P. K. Das ◽  
M. V. George
Keyword(s):  
Steady State ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Laser Flash
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