Light-Induced Mixed-Valence State of Fe II[Fe(CN) 5NO]·xH 2O

Yoshiyuki Morioka, Taka Aki Hisamitsu, Hidenari Inoue, Naoki Yoshioka, Hiroshi Tomizawa, Ei Khi Miki

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Abstract

A long-living metastable state is produced in Fe II[Fe(CN) 5NO]·xH 2O by an irradiation of 488 nm light at 200 K. A strong near-infrared band of about 10000 cm -1 and a v(CN) band at 2070 cm -1 that newly appear in the metastable state point to development of the mixed-valence state analogous to Prussian blue. An iron-to-nitrosyl charge transfer in pentacyanonitrosylferrate(2-), [Fe(CN) 5NO] 2-, explains the formation of the mixed-valence state, because the charge transfer causes a pair of iron(II) and iron(III) atoms bridged by CN - that has the same local structure as Prussian blue. In addition to the formation of the metastable state, the prolonged irradiation causes an irreversible change of Fe II[Fe(CN) 5NO]·H 2O and leads to the formation of a photoproduct. The photoproduct also has infrared spectra characteristic of the mixed-valence state. Mössbauer spectra of the photoproduct show that a low-spin iron ion in pentacyanonitrosylferrate(2-) is divalent and a high-spin iron outside of pentacyanonitrosylferrate(2-) is trivalent. Therefore, the charge-transfer between the two non-equivalent iron ions is thought to follow the intra-molecular charge transfer in pentacyanonitrosylferrate(2-).

Original languageEnglish
Pages (from-to)837-844
Number of pages8
JournalBulletin of the Chemical Society of Japan
Volume71
Issue number4
Publication statusPublished - 1998 Apr

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Iron
Charge transfer
Irradiation
Ions
Infrared radiation
Atoms
ferric ferrocyanide

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Morioka, Y., Hisamitsu, T. A., Inoue, H., Yoshioka, N., Tomizawa, H., & Miki, E. K. (1998). Light-Induced Mixed-Valence State of Fe II[Fe(CN) 5NO]·xH 2O. Bulletin of the Chemical Society of Japan, 71(4), 837-844.

Light-Induced Mixed-Valence State of Fe II[Fe(CN) 5NO]·xH 2O. / Morioka, Yoshiyuki; Hisamitsu, Taka Aki; Inoue, Hidenari; Yoshioka, Naoki; Tomizawa, Hiroshi; Miki, Ei Khi.

In: Bulletin of the Chemical Society of Japan, Vol. 71, No. 4, 04.1998, p. 837-844.

Research output: Contribution to journalArticle

Morioka, Y, Hisamitsu, TA, Inoue, H, Yoshioka, N, Tomizawa, H & Miki, EK 1998, 'Light-Induced Mixed-Valence State of Fe II[Fe(CN) 5NO]·xH 2O', Bulletin of the Chemical Society of Japan, vol. 71, no. 4, pp. 837-844.
Morioka Y, Hisamitsu TA, Inoue H, Yoshioka N, Tomizawa H, Miki EK. Light-Induced Mixed-Valence State of Fe II[Fe(CN) 5NO]·xH 2O. Bulletin of the Chemical Society of Japan. 1998 Apr;71(4):837-844.
Morioka, Yoshiyuki ; Hisamitsu, Taka Aki ; Inoue, Hidenari ; Yoshioka, Naoki ; Tomizawa, Hiroshi ; Miki, Ei Khi. / Light-Induced Mixed-Valence State of Fe II[Fe(CN) 5NO]·xH 2O. In: Bulletin of the Chemical Society of Japan. 1998 ; Vol. 71, No. 4. pp. 837-844.
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AB - A long-living metastable state is produced in Fe II[Fe(CN) 5NO]·xH 2O by an irradiation of 488 nm light at 200 K. A strong near-infrared band of about 10000 cm -1 and a v(CN) band at 2070 cm -1 that newly appear in the metastable state point to development of the mixed-valence state analogous to Prussian blue. An iron-to-nitrosyl charge transfer in pentacyanonitrosylferrate(2-), [Fe(CN) 5NO] 2-, explains the formation of the mixed-valence state, because the charge transfer causes a pair of iron(II) and iron(III) atoms bridged by CN - that has the same local structure as Prussian blue. In addition to the formation of the metastable state, the prolonged irradiation causes an irreversible change of Fe II[Fe(CN) 5NO]·H 2O and leads to the formation of a photoproduct. The photoproduct also has infrared spectra characteristic of the mixed-valence state. Mössbauer spectra of the photoproduct show that a low-spin iron ion in pentacyanonitrosylferrate(2-) is divalent and a high-spin iron outside of pentacyanonitrosylferrate(2-) is trivalent. Therefore, the charge-transfer between the two non-equivalent iron ions is thought to follow the intra-molecular charge transfer in pentacyanonitrosylferrate(2-).

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