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Photoinduced Valence Tautomerism in Cobalt Complexes Containing Semiquinone Anion as Ligand: Dynamics of the High-Spin [CoII(3,5-dtbsq)2] to Low-Spin [CoIII(3,5-dtbsq)(3,5-dtbcat)] Interconversion

Authors

  • David M. Adams,

    1. Department of Chemistry-0358, University of California at San Diego, La Jolla, CA 92093-0358 (USA). Telefax: Int. code + (619)534-5383
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  • Bulang Li,

    1. Department of Chemistry-0358, University of California at San Diego, La Jolla, CA 92093-0358 (USA). Telefax: Int. code + (619)534-5383
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  • Prof. John D. Simon,

    Corresponding author
    1. Department of Chemistry-0358, University of California at San Diego, La Jolla, CA 92093-0358 (USA). Telefax: Int. code + (619)534-5383
    • Department of Chemistry-0358, University of California at San Diego, La Jolla, CA 92093-0358 (USA). Telefax: Int. code + (619)534-5383
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  • Prof. David N. Hendrickson

    Corresponding author
    1. Department of Chemistry-0358, University of California at San Diego, La Jolla, CA 92093-0358 (USA). Telefax: Int. code + (619)534-5383
    • Department of Chemistry-0358, University of California at San Diego, La Jolla, CA 92093-0358 (USA). Telefax: Int. code + (619)534-5383
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  • This work was supported by the U. S. National Science Foundation (CHE-9306485 (J. D. S.). CHE-9115286 and CHE-9420322 (D. N. H.)) and the National Institutes of Health (HL13652 (D. N. H.)). 3,5-dtbsq = 3,5-di-tert-butylbenzosemiquinone; 3,5-dtbcat = 3,5-di-tert-butylcatecholate.

Abstract

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Picosecond laser-flash photolysis is employed to study intramolecular electron transfer and spinstate interconversion in a valence tautomeric cobalt complex. The CoIII form 1 of the complex is photoexcited to the high-spin CoII(semiquinone anion)2 form, whereupon relaxation back to the low-spin CoIII(semiquinone anion)(o-catecholate) state is monitored.

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