Journal
PHASE TRANSITIONS
Volume 75, Issue 7-8, Pages 779-785Publisher
TAYLOR & FRANCIS LTD
DOI: 10.1080/01411590290033895
Keywords
valence tautomerism; photo-induced electron transfer; long lifetime
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Photo-illumination effects have been measured for the compound [CoIII-LS(tmpda)(3,6-DBSQ)(3,6-DBCat)]. When the aforementioned compound was illuminated at 5 K, the magnetization value increased from mu(eff) = 1.87 to 2.03 mu(B). The absorption spectra after illumination show that the absorption band at around 730 nm, which is characteristic of the [CoII-HS(tmpda)(3,6-DBSQ)(2)] state, increased in intensity and that the charge transfer band from 3,6-DBCat to 3,6-DBSQ at 2500 nm was reduced in intensity. IR spectra show that the C-O stretching peak at 1279 cm(-1) is decreased in intensity. These results confirm that a photoinduced intra-molecular electron transfer, [CoIII-LS(tmpda)(3,6-DBSQ)(3,6-DBCat)]--> [CoII-HS(tmpda)(3,6-DBSQ)(2)], was induced. The lifetime of the metastable state at 5 K was 15 min. Furthermore, it was found that reverse valence tautomerism can be induced by exciting the CoII-HS to 3,6-DBSQ charge transfer band in metastable [CoII-HS(trnpda)(3,6-DBSQ)(2)].
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