Photo- and dehydration-induced charge transfer processes accompanied with spin transition on CoFe(CN)5NH3·6H2O

Z. Z. Gu, Yasuaki Einaga, O. Sato, A. Fujishima, K. Hashimoto

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

The coexistence of different valences of iron and cobalt in cobalt pentacyanoferrate, CoFe(CN)5NH3·6H2O, was confirmed by the infrared spectrum, in which two distinct peaks for the C-N stretch at 2162 cm-1 and 2117 cm-1 were assigned to CN in FeIII-CN-CoII and FeII-CN-CoIII respectively, and by the Mössbauer spectrum, in which FeIII and FeII exhibited doublets with different isomer shifts and different quadrupole splitting. Photo-irradiation of this compound with red light changed the population of these two electronic states due to the internal electron transfer from FeII to CoIII. As a result, the ferrimagnetic properties of this pentacyanometalate at low temperature can be changed by photo-irradiation similar to the case of the hexacyanometalate, K0.2Co1.4Fe(CN)6·6.9H2O reported previously (O. Sato et al., Science 272, 704 (1996)). Moreover, the fraction of these two electronic states in this pentacyanoferrate is sensitive to the number of water molecules, which induces a charge transfer from CoII and FeIII. As a result, dehydration increases the fraction of FeII-CN-CoIII and causes the compound to be paramagnetic even at low temperature.

Original languageEnglish
Pages (from-to)336-342
Number of pages7
JournalJournal of Solid State Chemistry
Volume159
Issue number2
DOIs
Publication statusPublished - 2001
Externally publishedYes

Fingerprint

Electronic states
Cobalt
Dehydration
dehydration
Charge transfer
cobalt
charge transfer
Irradiation
irradiation
electronics
Isomers
electron transfer
infrared spectra
isomers
Iron
quadrupoles
Infrared radiation
valence
iron
Temperature

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Photo- and dehydration-induced charge transfer processes accompanied with spin transition on CoFe(CN)5NH3·6H2O. / Gu, Z. Z.; Einaga, Yasuaki; Sato, O.; Fujishima, A.; Hashimoto, K.

In: Journal of Solid State Chemistry, Vol. 159, No. 2, 2001, p. 336-342.

Research output: Contribution to journalArticle

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AU - Sato, O.

AU - Fujishima, A.

AU - Hashimoto, K.

PY - 2001

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AB - The coexistence of different valences of iron and cobalt in cobalt pentacyanoferrate, CoFe(CN)5NH3·6H2O, was confirmed by the infrared spectrum, in which two distinct peaks for the C-N stretch at 2162 cm-1 and 2117 cm-1 were assigned to CN in FeIII-CN-CoII and FeII-CN-CoIII respectively, and by the Mössbauer spectrum, in which FeIII and FeII exhibited doublets with different isomer shifts and different quadrupole splitting. Photo-irradiation of this compound with red light changed the population of these two electronic states due to the internal electron transfer from FeII to CoIII. As a result, the ferrimagnetic properties of this pentacyanometalate at low temperature can be changed by photo-irradiation similar to the case of the hexacyanometalate, K0.2Co1.4Fe(CN)6·6.9H2O reported previously (O. Sato et al., Science 272, 704 (1996)). Moreover, the fraction of these two electronic states in this pentacyanoferrate is sensitive to the number of water molecules, which induces a charge transfer from CoII and FeIII. As a result, dehydration increases the fraction of FeII-CN-CoIII and causes the compound to be paramagnetic even at low temperature.

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