Controlled Light and Temperature Induced Valence Tautomerism in a Cobalt-o-Dioxolene Complex

Paul Raithby, Ludmila Leroy, Thiago Francisco, Helena Shepherd, Mark Warren, Lucy Saunders, David Shultz, Carlos Pinheiro

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The mononuclear cobalt complex of 3,5-di-tert-butylcathecolate and cyan-pyridine is a very versatile compound that displays valence tautomerism (VT) in the solid-state which is induced by temperature, light and hard X-rays and modulated by solvent in the crystal lattice. Here, we demonstrate the photo-induced valence tautomerism in benzene solvated crystals of such complex with a very high yield of metastable states using 450nm light, and also show evidence of the de-excitation of these photo-induced metastable states using red 660nm light. In our work we use single crystal X-ray diffraction as a probe for the VT and demonstrate the controlled use of hard X-rays using attenuated X-ray beams in order to control the X-ray induced VT interconversion. Our results point to a larger efficiency in the VT interconversion when d-d transitions are excited in comparison with charge transfer promotion.
Original languageEnglish
Article numberic-2021-006388
Pages (from-to)8665–8671
JournalInorganic Chemistry
Issue number12
Early online date4 Jun 2021
Publication statusPublished - 21 Jun 2021


  • Valence tautomerism
  • Cobalt o-semiquinone
  • Single-crystal
  • X-ray diffraction

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Spectroscopy


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