Thermal decomposition of Prussian blue analogues of the type Fe[Fe(CN)5NO]

Hidenari Inoue, Shuichi Narino, Naoki Yoshioka, Ekkehard Fluck

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

The structure and properties of the thermal decomposition products of Fe[Fe(CN)5NO] · x H2O (x = 5∼6) have been studied by Mössbauer and FT-IR spectroscopy, X-ray diffraction and conductivity measurements. The valence state and coordination environment of the iron ions change dramatically when the nitrosyl ligand is eliminated by heat-treatment under vacuum at 200 °C. The dark blue product obtained by heat-treatment under vacuum at 250 °C is characteristic of the mixed-valence state in Prussian blue analogues. The electrical conductivity of the dark blue product is higher by a factor of 103 than that of the starting material because of the mixed-valence state between Fe(III)[Fe(II)(CN)5] and Fe(II)[Fe(III)(CN)5]. Heat-treatment under vacuum at 350°C yields a new product Fe(II)[Fe(II)(CN)4] the crystal structure of which is different from that of the starting material. The electrical conductivity of the decomposition product obtained at 350 °C is about 105 times higher than that of the starting material.

Original languageEnglish
Pages (from-to)685-690
Number of pages6
JournalZeitschrift fur Naturforschung - Section B Journal of Chemical Sciences
Volume55
Issue number8
Publication statusPublished - 2000 Aug

Fingerprint

Pyrolysis
Heat treatment
Vacuum
Infrared spectroscopy
Iron
Crystal structure
Ions
Ligands
Decomposition
X ray diffraction
ferric ferrocyanide
Electric Conductivity

Keywords

  • Mixed-valence state
  • Prussian blue analogues
  • Thermal decomposition

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Thermal decomposition of Prussian blue analogues of the type Fe[Fe(CN)5NO]. / Inoue, Hidenari; Narino, Shuichi; Yoshioka, Naoki; Fluck, Ekkehard.

In: Zeitschrift fur Naturforschung - Section B Journal of Chemical Sciences, Vol. 55, No. 8, 08.2000, p. 685-690.

Research output: Contribution to journalArticle

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N2 - The structure and properties of the thermal decomposition products of Fe[Fe(CN)5NO] · x H2O (x = 5∼6) have been studied by Mössbauer and FT-IR spectroscopy, X-ray diffraction and conductivity measurements. The valence state and coordination environment of the iron ions change dramatically when the nitrosyl ligand is eliminated by heat-treatment under vacuum at 200 °C. The dark blue product obtained by heat-treatment under vacuum at 250 °C is characteristic of the mixed-valence state in Prussian blue analogues. The electrical conductivity of the dark blue product is higher by a factor of 103 than that of the starting material because of the mixed-valence state between Fe(III)[Fe(II)(CN)5] and Fe(II)[Fe(III)(CN)5]. Heat-treatment under vacuum at 350°C yields a new product Fe(II)[Fe(II)(CN)4] the crystal structure of which is different from that of the starting material. The electrical conductivity of the decomposition product obtained at 350 °C is about 105 times higher than that of the starting material.

AB - The structure and properties of the thermal decomposition products of Fe[Fe(CN)5NO] · x H2O (x = 5∼6) have been studied by Mössbauer and FT-IR spectroscopy, X-ray diffraction and conductivity measurements. The valence state and coordination environment of the iron ions change dramatically when the nitrosyl ligand is eliminated by heat-treatment under vacuum at 200 °C. The dark blue product obtained by heat-treatment under vacuum at 250 °C is characteristic of the mixed-valence state in Prussian blue analogues. The electrical conductivity of the dark blue product is higher by a factor of 103 than that of the starting material because of the mixed-valence state between Fe(III)[Fe(II)(CN)5] and Fe(II)[Fe(III)(CN)5]. Heat-treatment under vacuum at 350°C yields a new product Fe(II)[Fe(II)(CN)4] the crystal structure of which is different from that of the starting material. The electrical conductivity of the decomposition product obtained at 350 °C is about 105 times higher than that of the starting material.

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