Emission from Regioisomeric Bis(phenylethynyl)benzenes during Pulse Radiolysis

  • Shingo Samori
    The Institute of Scientific and Industrial Research (SANKEN), Osaka University, Mihogaoka 8-1, Ibaraki, Osaka 567-0047, Japan, and Department of Chemistry and the Materials Science Institute, University of Oregon, Eugene, Oregon 97403-1253
  • Sachiko Tojo
    The Institute of Scientific and Industrial Research (SANKEN), Osaka University, Mihogaoka 8-1, Ibaraki, Osaka 567-0047, Japan, and Department of Chemistry and the Materials Science Institute, University of Oregon, Eugene, Oregon 97403-1253
  • Mamoru Fujitsuka
    The Institute of Scientific and Industrial Research (SANKEN), Osaka University, Mihogaoka 8-1, Ibaraki, Osaka 567-0047, Japan, and Department of Chemistry and the Materials Science Institute, University of Oregon, Eugene, Oregon 97403-1253
  • Torben Ryhding
    The Institute of Scientific and Industrial Research (SANKEN), Osaka University, Mihogaoka 8-1, Ibaraki, Osaka 567-0047, Japan, and Department of Chemistry and the Materials Science Institute, University of Oregon, Eugene, Oregon 97403-1253
  • Aaron G. Fix
    The Institute of Scientific and Industrial Research (SANKEN), Osaka University, Mihogaoka 8-1, Ibaraki, Osaka 567-0047, Japan, and Department of Chemistry and the Materials Science Institute, University of Oregon, Eugene, Oregon 97403-1253
  • Brittany M. Armstrong
    The Institute of Scientific and Industrial Research (SANKEN), Osaka University, Mihogaoka 8-1, Ibaraki, Osaka 567-0047, Japan, and Department of Chemistry and the Materials Science Institute, University of Oregon, Eugene, Oregon 97403-1253
  • Michael M. Haley
    The Institute of Scientific and Industrial Research (SANKEN), Osaka University, Mihogaoka 8-1, Ibaraki, Osaka 567-0047, Japan, and Department of Chemistry and the Materials Science Institute, University of Oregon, Eugene, Oregon 97403-1253
  • Tetsuro Majima
    The Institute of Scientific and Industrial Research (SANKEN), Osaka University, Mihogaoka 8-1, Ibaraki, Osaka 567-0047, Japan, and Department of Chemistry and the Materials Science Institute, University of Oregon, Eugene, Oregon 97403-1253

書誌事項

公開日
2009-04-14
資源種別
journal article
DOI
  • 10.1021/jo900494j
公開者
American Chemical Society (ACS)

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説明

Emission from charge recombination between radical cations and anions of a series of regioisomeric 1,4-, 1,3-, and 1,2-bis(phenylethynyl)benzenes (bPEBs) substituted by various electron donor and/or acceptor groups was measured during pulse radiolysis in benzene (Bz). The formation of bPEB in the excited singlet state ((1)bPEB*) can be attributed to the charge recombination between bPEB(*+) and bPEB(*-), which are initially generated from the radiolytic reaction. This mechanism is reasonably explained by the relationship between the annihilation enthalpy change (-DeltaH(o)) for the charge recombination of bPEB(*+) and bPEB(*-) and excitation energy of (1)bPEB*. Since the degree of the pi-conjugation in the S(1) state and HOMO-LUMO levels of bPEB change with the substitution pattern of phenylacetylene groups on the central benzene ring and the various kinds of donor and/or acceptor group, the fine-tuning of the emission color and intensity of bPEB can be easily carried out during pulse radiolysis in Bz. For donor-acceptor-substituted bPEB, it was found that the difference in the charge transfer conjugated pathways between donor and acceptor substituents (linear-, cross-, and "bent"-conjugated pathways) strongly influenced the HOMO-LUMO energy gap.

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