Photoinduced Solid State Conversion of a Radical σ-Dimer to a π-Radical Pair.

Irradiation in the solid state of the hypervalent 4c-6e S···S–S···S bridged σ-dimer of a bisdithiazolyl radical leads to its photodissociation into a pair of π-radicals. The transformation has been monitored by optical spectroscopy, single crystal X-ray diffraction, and magnetic susceptibility measu...

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Published in:Journal of the American Chemical Society Vol. 135; no. 42; pp. 15674 - 15678
Main Authors: Hoa Phan, Lekin, Kristina, Winter, Stephen M., Oak1ey, Richard T., Shatruk, Michael
Format: Article
Published: American Chemical Society 10/23/2013
Subjects:
Online Access:View this record in EBSCOhost
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      dt: 10/23/2013
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      pub: American Chemical Society
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        10.1021/ja4055806
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        atl: Photoinduced Solid State Conversion of a Radical σ-Dimer to a π-Radical Pair.
      aug:
        au:
          Hoa Phan
          Lekin, Kristina
          Winter, Stephen M.
          Oak1ey, Richard T.
          Shatruk, Michael
        affil:
          Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, United States
          Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada
      su:
        Dimers
        Geminate pairs (Molecules)
        Solid state chemistry
        Hypervalence (Theoretical chemistry)
        Photodissociation
        Single crystals
        X-ray diffraction
        Magnetic susceptibility
      sug:
        subj:
          Dimers
          Geminate pairs (Molecules)
          Solid state chemistry
          Hypervalence (Theoretical chemistry)
          Photodissociation
          Single crystals
          X-ray diffraction
          Magnetic susceptibility
      ab: Irradiation in the solid state of the hypervalent 4c-6e S···S–S···S bridged σ-dimer of a bisdithiazolyl radical leads to its photodissociation into a pair of π-radicals. The transformation has been monitored by optical spectroscopy, single crystal X-ray diffraction, and magnetic susceptibility measurements. As a result of the large electronic reorganization involved in the dimer-to-radical interconversion, the photogenerated S = 1/2 radical state is remarkably thermally stable, persisting to 242 K before reverting to the S = 0 dimer.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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