Solvation of benzophenone anion radical in ethanol and ethanol/2-methyltetrahydrofuran mixture

Journal Article · Thu Jan 28 04:00:00 EST 1988 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100313a052· OSTI ID:5248634

Ichikawa, T; Ishikawa, Y; Yoshida, H

The electron spin-echo modulations and the absoprtion spectra of benzophenone anion radicals generated by ..gamma..-irradiation in the glassy matrices of ethanol and ethanol2-methyltetrahydrofuran mixtures have been measured for elucidating the mechanism of spectral shift observed during the solvation of the anion radicals in alcohols. The anion radical generated at 4.2 K in the ethanol matrix maintains the same solvation structure as that of neutral benzophenone. At 77 K ethanol molecules solvate the anion radical by orienting the O-H dipoles toward the anion radical. The anion radical is hydrogen-bonded by two ethanol molecules through the p/sub z/ orbital on the benzophenone oxygen which composes the ..pi.. orbitals of anion radical. Three kinds of anion radicals are observed in the mixed matrix at 77 K. Two of them are essentially the same as those observed in the ethanol matrix at 4.2 and 77 K. The third has the absorption maximum at 700 nm and is attributed to the anion radical hydrogen-bonded by one ethanol molecule through the p/sub z/ orbital. It is concluded that the spectral shift observed in alcohols is caused by the stabilization of a SOMO ..pi..* orbital induced by the hydrogen bonding with the (RO)H--O--H(OR) angle perpendicular to the molecular plane of the anion radical

• Research Organization: Hokkaido Univ., Sapporo, Japan
• OSTI ID: 5248634
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 92:2; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400600* -- Radiation Chemistry
ABSORPTION SPECTROSCOPY
ACOUSTIC ESR
ALCOHOLS
ANIONS
BENZOPHENONE
CHARGED PARTICLES
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTIONS
CHEMISTRY
DATA
DECOMPOSITION
ELECTRON SPIN RESONANCE
ETHANOL
EXPERIMENTAL DATA
FURANS
HETEROCYCLIC COMPOUNDS
HYDROXY COMPOUNDS
INFORMATION
IONS
KETONES
MAGNETIC RESONANCE
MTHF
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
RADIATION CHEMISTRY
RADIATION EFFECTS
RADICALS
RADIOLYSIS
RESONANCE
SPECTRA
SPECTROSCOPY
TETRAHYDROFURAN
ULTRALOW TEMPERATURE
VERY LOW TEMPERATURE
VISIBLE SPECTRA