Natures of π→π* and n→π* Transitions of 4, 4'-Dimethylbenzil

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  • Hoshi Toshinko
    Department of Chemistry, College of Science and Engineering, Aoyama Gakuin University;
  • YAMADA Yasunori
    Department of Chemistry, College of Science and Engineering, Aoyama Gakuin University;
  • FUKUMORI Asami
    Department of Chemistry, College of Science and Engineering, Aoyama Gakuin University;
  • OKUBO Jun
    Department of Natural Science for General Education, Faculty of Engineering, Tokyo Denki University;
  • KOBAYASHI Michio
    Department of Chemistry, Nagaoka University of Technology ;
  • INOUE Hiroyasu
    Department of Applied Chemistry, Faculty of Technology, Kanagawa University;

Bibliographic Information

Other Title
  • 4,4'-ジメチルベンジルのπ-π*およびn-π*遷移の性格
  • Natures of .PI..RAR..PI.* and n.RAR..PI.* Transitions of 4,4'-Dimethylbenzil.

Description

4, 4'-Dimethylbenzil shows four n→π* transitions at 381.0, 358.5, 338.0 and 330 nm in EPA (ether: isopentane: ethanol=5: 5: 2) at 101 K. From configuration analysis, it is found that 381.0 and 358.5 nm bands can be assigned to the n→π* transitions localized separately on the two benzoyl moieties, and the 338.0 and 330 nm bands to the n-, 27-* transitions, having intramolecular CT characters, from the n orbital of the oxygen atom to the 7r* orbital belonging to the different benzoyl moiety. The 232.5 nm band, observed in the PE(polyethylene)film at 101 K, has mixed natures of the n→π* transition with intramolecular CT character and the nearby intense π→π* one. The polarized absorption spectrum, measured in the stretched PE film at 101K, shows that the intense, π→π*band, appearing in the wavelength region 250-320 nm, is composed of the three electronic bands at 293, 278.5 and 272 nm, whic h can be assigned to the S5←S0, S7←S0 and S8←S0 transitions, respectively. Splitting features of the above mentioned n→π* transitions indicate that the two n orbitals interact significantly. The n orbital also interacts with the 7r orbital belonging to the different benzoyl moiety.

Journal

  • NIPPON KAGAKU KAISHI

    NIPPON KAGAKU KAISHI 1992 (12), 1440-1445, 1992-12-10

    The Chemical Society of Japan

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