Journal of Physical Chemistry p. 9353 - 9359 (1992)
Update date:2022-08-29
Topics:
Yamaji, Minoru
Sekiguchi, Tetuhiro
Hoshino, Mikio
Shizuka, Haruo
A laser flash photolysis study at 355 nm has been carried out on acetonitrile-water (4:1 v/v) mixtures of the methoxynaphthalene-benzophenone-H2SO4 system.It is found that the proton-assisted photoionization reaction of triplet 1- and 2-methoxynaphthalene (ROMe) produced by triplet sensitization of benzophenone (BP) effectively occurs to produce the corresponding methoxynaphthalene cation radical (ROMe(1+.)) and benzophenone ketyl radical (>C(.)OH).The triplet energy-transfer reaction from triplet benzophenone (3BP*) to ROMe takes place as the primary event to produce triplet methoxynaphthalene (3ROMe*).The 1:1 triplet exciplex 3(ROMe...>CO)* having a weak charge-transfer structure is readily formed between 3ROMe* and BP with the equilibrium constants K1 (10.1 M-1 for 1ROMe; 4.0 M-1 for 2ROMe at 290 K).In the presence of protons, the triplet protonated exciplex 3(ROMe...>C(1+)OH)* is also produced by protonation to 3(ROMe...>CO)*.Subsequently, the intraexciplex electron-transfer reaction in 3(ROMe...>C(1+)OH)* takes place effectively, resulting in the formation of ROMe(1+.) and >C(.)OH.The presence of protons in the ROMe-BP system assists the photoionization of ROMe with the much lower energy (triplet energy of ROMe) than its ionization potential.The reaction mechanism is discussed in detail.
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