title: One-electron oxidation of alcohols by the 1,3,5-trimethoxybenzene radical cation in the excited state during two-color two-laser flash photolysis.
abstract: One-electron oxidation of alcohols such as methanol, ethanol, and 2-propanol by 1,3,5-trimethoxybenzene radical cation (TMB*+) in the excited state (TMB*+*) was observed during the two-color two-laser flash photolysis. TMB*+ was formed by the photoinduced bimolecular electron-transfer reaction from TMB to 2,3,5,6-tetrachlorobenzoquinone (TCQ) in the triplet excited-state during the first 355-nm laser flash photolysis. Then, TMB*+* was generated from the selective excitation of TMB*+ during the second 532 nm laser flash photolysis. Hole transfer rate constants from TMB*+* to methanol, ethanol, and 2-propanol were calculated to be (5.2 +/- 0.5) x 10(10), (1.4 +/- 0.3) x 10(11), and (3.2 +/- 0.6) x 10(11) M-1 s-1, respectively. The order of the hole transfer rate constants is consistent with oxidation potentials of alcohol. Formation of TCQH radical (TCQH*) with a characteristic absorption peak at 435 nm was observed in the microsecond time scale, suggesting that deprotonation of the alcohol radical cation occurs after the hole transfer and that TCQ radical anion (TCQ*-), generated together with TMB*+ by the photoinduced electron-transfer reaction, reacts with H+ to give TCQH*.
authors.affiliation: The Institute of Scientific and Industrial Research (SANKEN), Osaka University, Mihogaoka 8-1, Ibaraki, Osaka 567-0047, Japan.
authors.forename: Xichen
authors.initials: X
authors.lastname: Cai
authors.forename: Masanori
authors.initials: M
authors.lastname: Sakamoto
authors.forename: Mamoru
authors.initials: M
authors.lastname: Fujitsuka
authors.forename: Tetsuro
authors.initials: T
authors.lastname: Majima
mesh_terms: D000438:Alcohols / Q000737:chemistry*; D002412:Cations / Q000737:chemistry; D004583:Electrons; D005609:Free Radicals / Q000737:chemistry; D007834:Lasers; D010084:Oxidation-Reduction; D010696:Phloroglucinol / Q000031:analogs & derivatives* / Q000737:chemistry; D010782:Photolysis
chemical_list: D000438:Alcohols; D002412:Cations; D005609:Free Radicals; C015560:1,3,5-trimethoxybenzene; D010696:Phloroglucinol