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J Am Chem Soc. 2013 Oct 23;135(42):15674-7. doi: 10.1021/ja4055806. Epub 2013 Oct 9.

Photoinduced solid state conversion of a radical σ-dimer to a π-radical pair.

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1
Department of Chemistry and Biochemistry, Florida State University , Tallahassee, Florida 32306, United States.

Abstract

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.

PMID:
24107231
DOI:
10.1021/ja4055806
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