Mechanism and relaxation kinetics of photo-induced valence tautomerism of [Co(phen)(3,5-DBSQ)2]·C6H5Cl

Aili Cui, Kazuyuki Takahashi, Akira Fujishima, Osamu Sato

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38 Citations (Scopus)


Photo-illumination effects have been measured for [CoIII-LS (phen)(3,5-DBSQ)(3,5-DBCat)]·C6H5Cl, where LS, phen, 3,5-DBSQ and 3,5-DBCat denote low-spin, 1,10-phenanthroline, 3,5-di- tert -butyl-1,2-semiquinonate and 3,5-di- tert -butyl-1,2-catecholate, respectively. When the Co compound was illuminated at 5 K, the magnetization value, μ eff increased from 1.7 to 2.7 μ B. The UV-Vis absorption spectra after illumination show that the absorption band at around 800 nm, characteristic of the [CoII-HS(phen) (3,5-DBSQ)2] state (HS denotes high-spin), increased and the charge transfer band from 3,5-DBCat to 3,5-DBSQ at 2500 nm was reduced. IR spectra show that the C-O stretching peak at 1280 cm-1 is significantly decreased. These results confirm that a photo-induced intra-molecular electron transfer, [CoIII-LS(phen)(3,5-DBSQ)(3,5-DBCat)]·C6 H5Cl↔[CoII-HS(phen)(3,5-DBSQ)2] ·C6H5Cl, was induced by 532 or 830 nm light. The relaxation kinetics of valence tautomerism was studied. For T≥25 K, kVT0=0.205 s-1 and Ea=110.38 cm-1. Below 25 K, the rate constant for the valence tautomeric relaxation as T approaches the 0 K, which suggests that tunneling is the predominant mechanism for the relaxation.

Original languageEnglish
Pages (from-to)69-73
Number of pages5
JournalJournal of Photochemistry and Photobiology A: Chemistry
Issue number2-3
Publication statusPublished - Oct 1 2004
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • General Chemistry
  • General Chemical Engineering
  • General Physics and Astronomy


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