Title of article :
Optical Charge-Transfer in Iron(III)hexacyanoferrate(II): Electro-intercalated Cations Induce Lattice-Energy-Dependent Ground-State Energies
Author/Authors :
Rosseinsky، David R. نويسنده , , Lim، Hanyong نويسنده , , Jiang، Hongjin نويسنده , , Chai، Jian Wei نويسنده ,
Issue Information :
روزنامه با شماره پیاپی سال 2003
Abstract :
The maximum of the color-conferring charge-transfer (CT) band in Prussian Blue (PB) varies with the electrochemically introduced cation Mz+ incorporated (as "supernumerary") for charge neutrality, and the dependence on particular properties of the Mz+ 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 Mz+ ferrocyanides (that provide direct indicators of the intra-lattice Mz+-[FeII(CN)6]4- interactions) show a strong correlation with the spectral shifts. The determining interaction of Mz+ with ferrocyanide within PB is enhanced in some cases by the accessibility of Mz+ oxidation states (plus-minus) 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 Mz+ within the lattices was confirmed by XPS.
Keywords :
Oscillations , Complete oxidation , Metal catalysts , Partial oxidation , Methane oxidation
Journal title :
INORGANIC CHEMISTRY
Journal title :
INORGANIC CHEMISTRY