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Optical Charge-Transfer in Iron(III)hexacyanoferrate(II): Electro-intercalated Cations Induce Lattice-Energy-Dependent Ground-State Energies

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David R. Rosseinsky,*^† Hanyong Lim,^†^‖ Hongjin Jiang,^‡ and Jian Wei Chai^§

Singapore Institute of Manufacturing Technology, 71 Nanyang Drive, Singapore 638075, Finisar (Singapore) Pte Ltd., 100 Collyer Quay No. 19-08, Singapore 049315, and Institute of Materials Research and Engineering, 3 Research Link, Singapore 117602

Inorg. Chem., 2003, 42 (19), pp 6015–6023

DOI: 10.1021/ic020575s

Publication Date (Web): August 28, 2003

Section:

Electrochemistry

Abstract

The maximum of the color-conferring charge-transfer (CT) band in Prussian Blue (PB) varies with the electrochemically introduced cation M^z⁺ incorporated (as “supernumerary”) for charge neutrality, and the dependence on particular properties of the M^z⁺ has been sought. With alkali-metal ions, the CT-maximum shifts are in the same sequence as the PB mass changes on M⁺ insertion; the effect on the CT ground state of the intra-lattice interaction of an M⁺ with the ferrocyanide CN^- moiety (competing with cation hydration), is then implicated in shifts of the maxima, as the ferrocyanide is the donor center in the optical CT. More definitely, for M²⁺ and Ag⁺, solubility-products of the insoluble M^z⁺ ferrocyanides (that provide direct indicators of the intra-lattice M^z⁺−[Fe^II(CN)₆]⁴^- interactions) show a strong correlation with the spectral shifts. The determining interaction of M^z⁺ with ferrocyanide within PB is enhanced in some cases by the accessibility of M^z⁺ oxidation states ± 1 different from the common values. PB lattice energies and the ground states of the optical CTs thus appear closely interlinked. The electrochemical uptake of appreciable amounts of the M^z⁺ within the lattices was confirmed by XPS.

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This article has been cited by 5 ACS Journal articles (5 most recent appear below).

Identification of Processes Associated with Different Iron Sites in the Prussian Blue Structure by in Situ Electrochemical, Gravimetric, and Spectroscopic Techniques in the dc and ac Regimes
Jerónimo Agrisuelas, José J. García-Jareño, and Francisco Vicente
The Journal of Physical Chemistry C2012 116 (2), 1935-1947
- Identification of Processes Associated with Different Iron Sites in the Prussian Blue Structure by in Situ Electrochemical, Gravimetric, and Spectroscopic Techniques in the dc and ac Regimes
  Jerónimo Agrisuelas, José J. García-Jareño, and Francisco Vicente
  The Journal of Physical Chemistry C2012 116 (2), 1935-1947
  The physicochemical properties of Prussian blue films are strongly dependent on the ratio Fe3+/Fe2+ in the structure. This ratio can be modulated by electrochemical techniques such as cyclic voltammetry, and some information about physicochemical ...
  Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
Innovative Combination of Three Alternating Current Relaxation Techniques: Electrical Charge, Mass, and Color Impedance Spectroscopy. Part I: The Tool
Jeronimo Agrisuelas, Jose Juan García-Jareño, David Gimenez-Romero and Francisco Vicente
The Journal of Physical Chemistry C2009 113 (19), 8430-8437
- Innovative Combination of Three Alternating Current Relaxation Techniques: Electrical Charge, Mass, and Color Impedance Spectroscopy. Part I: The Tool
  Jeronimo Agrisuelas, Jose Juan García-Jareño, David Gimenez-Romero and Francisco Vicente
  The Journal of Physical Chemistry C2009 113 (19), 8430-8437
  Technical details concerning the simultaneous acquisition of three impedance functions (electrochemical impedance spectroscopy, alternating current electrogravimetry or mass impedance, and alternating current colorimetry or color impedance) are presented. ...
  Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
Synthesis of Nanoscale Co₃[Co(CN)₆]₂ in Reverse Microemulsions
Daniel H. M. Buchold and Claus Feldmann
Chemistry of Materials2007 19 (14), 3376-3380
- Synthesis of Nanoscale Co₃[Co(CN)₆]₂ in Reverse Microemulsions
  Daniel H. M. Buchold and Claus Feldmann
  Chemistry of Materials2007 19 (14), 3376-3380
  The aim of this study is the synthesis of nanoscale, nonagglomerated, and redispersible Co3[Co(CN)6]2 nanoparticles via a microemulsion approach. Furthermore, the micellar system is heated to reflux to enhance materials crystallinity. Crystallinity, ...
  Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
Band Gap Variation in Prussian Blue via Cation-Induced Structural Distortion
Jacek C. Wojdeł and Stefan T. Bromley
The Journal of Physical Chemistry B2006 110 (48), 24294-24298
- Band Gap Variation in Prussian Blue via Cation-Induced Structural Distortion
  Jacek C. Wojdeł and Stefan T. Bromley
  The Journal of Physical Chemistry B2006 110 (48), 24294-24298
  The charge-transfer band gap of the iron cyanide framework material Prussian Blue and its dependence on the type and location of the charge-compensating interstitial cations (K+, Rb+, Cs+) are investigated via periodic density functional (DF) ...
  Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
Thermodynamic Clarification of the Curious Ferric/Potassium Ion Exchange Accompanying the Electrochromic Redox Reactions of Prussian Blue, Iron(III) Hexacyanoferrate(II)
David R. Rosseinsky, Leslie Glasser, and H. Donald Brooke Jenkins
Journal of the American Chemical Society2004 126 (33), 10472-10477
- Thermodynamic Clarification of the Curious Ferric/Potassium Ion Exchange Accompanying the Electrochromic Redox Reactions of Prussian Blue, Iron(III) Hexacyanoferrate(II)
  David R. Rosseinsky, Leslie Glasser, and H. Donald Brooke Jenkins
  Journal of the American Chemical Society2004 126 (33), 10472-10477
  The recent Glasser−Jenkins method for lattice-energy prediction, applied to an examination of the solid-state thermodynamics of the cation exchanges that occur in electrochromic reactions of Prussian Blue, provides incisive thermodynamic clarification of ...
  Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links

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History

Published In Issue September 22, 2003
Received September 23, 2002

Select a CAS section from the 5 main topical divisions below:

Article

Optical Charge-Transfer in Iron(III)hexacyanoferrate(II): Electro-intercalated Cations Induce Lattice-Energy-Dependent Ground-State Energies

Abstract

Citing Articles

Identification of Processes Associated with Different Iron Sites in the Prussian Blue Structure by in Situ Electrochemical, Gravimetric, and Spectroscopic Techniques in the dc and ac Regimes

Identification of Processes Associated with Different Iron Sites in the Prussian Blue Structure by in Situ Electrochemical, Gravimetric, and Spectroscopic Techniques in the dc and ac Regimes

Innovative Combination of Three Alternating Current Relaxation Techniques: Electrical Charge, Mass, and Color Impedance Spectroscopy. Part I: The Tool

Innovative Combination of Three Alternating Current Relaxation Techniques: Electrical Charge, Mass, and Color Impedance Spectroscopy. Part I: The Tool

Synthesis of Nanoscale Co₃[Co(CN)₆]₂ in Reverse Microemulsions

Synthesis of Nanoscale Co₃[Co(CN)₆]₂ in Reverse Microemulsions

Band Gap Variation in Prussian Blue via Cation-Induced Structural Distortion

Band Gap Variation in Prussian Blue via Cation-Induced Structural Distortion

Thermodynamic Clarification of the Curious Ferric/Potassium Ion Exchange Accompanying the Electrochromic Redox Reactions of Prussian Blue, Iron(III) Hexacyanoferrate(II)