Photochemical reactions of triplet state of safranine-T studied by transient absorption spectroscopy in visible/near-IR regions
D.-M. Islam, Shafiqul; Fujitsuka, Mamoru; Ito, Osamu
Журнал:
Physical Chemistry Chemical Physics
Дата:
1999
Аннотация:
Properties and reactivities of the triplet state of safranine-T [<sup>3</sup>(STH<sup>+</sup>)*] have been studied by following the transient absorption bands measured with nanosecond laser flash photolysis. Solvent effect was found in the lifetime and Tâ T annihilation rate constant (k TT) of <sup>3</sup>(STH<sup>+</sup>)*; the lifetime in ethanol is quite long and k TT in water is too small to observe. For electron transfer of <sup>3</sup>(STH<sup>+</sup>)* with various electron donors, the reaction rate constants decrease with the oxidation potentials of the donors along with the Rehemâ Weller relation. For the high electron-donors, the reaction rate constants were found to be solvent viscosity dependent rather than dielectric constants, suggesting the triplet exciplex formation prior to electron transfer. Different reactivities of <sup>3</sup>(STH<sup>+</sup>)* towards H-abstraction reactions have been observed depending on the nature of H-atom donors: with phenols, the reaction center of the triplet states has a highly electrophilic nature, while it has a nucleophilic character with respect to thiophenols, suggesting that the reactive position of <sup>3</sup>(STH<sup>+</sup>)* changes with the substrates.
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