Photochemistry of ketones in solution. XXXVII. Flash photolysis of Michler's ketone in solution. Rate constants for decay and triplet excimer formation

1973 ◽  
Vol 95 (3) ◽  
pp. 986-988 ◽  
Author(s):  
David I. Schuster ◽  
Marc D. Goldstein
Keyword(s):  
Rate Constants ◽  
Flash Photolysis ◽  
Solution Rate ◽  
Excimer Formation ◽  
Triplet Excimer

Laser flash-photolysis of methylene blue solutions

1979 ◽  
Vol 44 (7) ◽  
pp. 2015-2023 ◽  
Author(s):  
Viktor Řehák ◽  
Jaroslav Poskočil
Keyword(s):  
Methylene Blue ◽  
Electron Transfer ◽  
Energy Transfer ◽  
Rate Constants ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Laser Flash ◽  
Kinetic Measurements ◽  
Methanolic Solution ◽  
Triplet Excimer

Besides population and relaxation of T1 state of methylene blue in methanolic solution it has been possible to observe increase and decomposition of a transient with longer lifetime which is probably a triplet excimer of the dyestuff. Kinetic measurements have enabled to determine the lifetime of the T1 excimer, rate constants of energy-transfer to oxygen and electron-transfer from pyrrolidine to T1 of the dyestuff.

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,

Remarkable kinetic stability of α-thiocarbamoyl substituted 4-methoxybenzylcations

1998 ◽  
Vol 76 (12) ◽  
pp. 1910-1915 ◽  
Author(s):  
Robert A McClelland ◽  
Victoria E Licence ◽  
John P Richard ◽  
Kathleen B Williams ◽  
Shrong-Shi Lin
Keyword(s):  
Key Words ◽  
Strong Interaction ◽  
Rate Constants ◽  
Flash Photolysis ◽  
Visible Absorption ◽  
Methyl Group ◽  
Thioamide Group ◽  
Azide Ion ◽  
Uv Visible ◽  
Leaving Groups

4-Methoxybenzyl cations bearing α-(N,N-dimethylcarbamoyl) and α-(N,N-dimethylthiocarbamoyl) substituents have been generated photochemically upon irradiation of precursors with pentafluorobenzoate or 4-methoxybenzoate leaving groups. The ions have been observed with flash photolysis in 40:60 acetonitrile:water and in 50:50 methanol:water, and rate constants were measured for their decay in solvent alone and for their capture by azide ion. The cations so studied and their lifetimes in 40% acetonitrile are 6, ArC+H-CONMe2, 0.6 μs; 2, ArC+H-CSNMe2, 7 ms; and 4, ArC+(CH3)-CSMe2, 6 ms, where Ar = 4-MeOC6H4. The cation 4 reacts with solvent by elimination of a proton from the α-methyl group, and the rate constant for solvent addition must be less than 1 s-1. The CSNMe2 substituted cations are 105-107-fold longer lived than analogs where the thioamide group has been replaced with an α-methyl. The UV-visible absorption spectra of these two cations also show significant differences from those of typical 4-methoxybenzyl cations. Thus, both the lifetimes and spectra point to a strong interaction of the benzylic centre with the thioamide group. Key words: flash photolysis, thiocarbamoyl stabilized carbocation, photosolvolysis.

Mechanistic studies of aromatic ketone-sensitized photoreduction of bis(acetylacetonato)copper(II)

1983 ◽  
Vol 61 (5) ◽  
pp. 801-808 ◽  
Author(s):  
Yuan L. Chow ◽  
Gonzalo E. Buono-Core ◽  
Bronislaw Marciniak ◽  
Carol Beddard
Keyword(s):  
Rate Constant ◽  
Rate Constants ◽  
Flash Photolysis ◽  
Decay Rates ◽  
Polynuclear Aromatic Hydrocarbons ◽  
Aromatic Ketone ◽  
Quantum Yields ◽  
Triplet States ◽  
Quenching Rate ◽  
Triplet Energy

Bis(acetylacetonato)copper(II), Cu(acac)2, quenches triplet excited states of ketones and polynuclear aromatic hydrocarbons efficiently, but only aromatic ketones with high triplet energy successfully sensitize photoreduction of Cu(acac)2 in alcohols under nitrogen to give derivatives of aeetylacetonatocopper(I), Cu(acac). For the triplet state benzophenone-sensitized photoreduction of Cu(acac)2, the quantum yields of photoreduction (ΦC) and those of benzophenone disappearance (ΦB) were determined in methanol with various concentrations of Cu(acac)2. The values of the quenching rate constant, kq, determined from these two types of monitors on the basis of the proposed mechanism were in good agreement (6.89 ~ 7.35 × 109 M−1 s−1). This value was higher, by a factor of about two, than that obtained from the monitor of the benzophenone triplet decay rates generated by flash photolysis in the presence of Cu(acac)2. The quenching rate constants of various aromatic ketone and hydrocarbon triplet states by Cu(acac)2 were determined by flash photolysis to be in the order of the diffusion rate constant and the quantum yields of these photoreductions were found to be far from unity. Paramagnetic quenching, with contributions of electron exchange and charge transfer, was proposed as a possible quenching mechanism. For a series of aromatic ketone sensitizers with higher triplet energy, this mechanism was used to rationalize the observed high quenching rate constants in contrast to the low quantum yields of photoreduction.

“Fast” triplet excimer formation in fluid solutions of dinaphthylalkanes

1981 ◽  
Vol 77 (2) ◽  
pp. 294-298 ◽  
Author(s):  
D. Webster ◽  
J.F. Baugher ◽  
Bee T. Lim ◽  
E.C. Lim
Keyword(s):  
Excimer Formation ◽  
Triplet Excimer
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