Electronic interaction in an outer-sphere mixed-valence double salt: a polarized neutron diffraction study of K(3)(MnO(4))(2).

The mixed-valence double salt K(3)(MnO(4))(2) crystallizes in space group P2(1)/m with Z = 2. The manganese centers Mn1 and Mn2 constitute discrete "permanganate", [Mn(VII)O(4)](-), and "manganate", [Mn(VI)O(4)](2-), ions, respectively. There is a spin-ordering transition to an antiferromagnetic state at ca.

Thermodynamic clarification of the curious ferric/potassium ion exchange accompanying the electrochromic redox reactions of prussian blue, iron(III) hexacyanoferrate(II).

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 an ill-understood ion exchange that accompanies particularly the early electrochromic cycles. A volume of 0.246 +/- 0.

Optical charge-transfer in iron(III)hexacyanoferrate(II): electro-intercalated cations induce lattice-energy-dependent ground-state energies.

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.

Charge-transfer band shifts in iron(III) hexacyanoferrate(II) by electro-intercalated cations via ground state-energy/lattice-energy link.

It is currently important to achieve and understand adjustments of optical properties: "guest cation" induced CT spectral shifts in Prussian Blue are shown to be driven (via its specific effect on the Fe(CN)6 CT-donor entity) by the cation lattice-energy interaction, as inferred from microgravimetry of introduced alkali-metal ions, and from independent solubility correlations for other intercalated cations.