The Foripal Potentials of Solid Metal Hexacyanometalates

摘要

We report here on the first formal potentials of a series of solid metal hexucyanometalates (M~+ )_n M'[M"(CN)_6] (M~+ = Li~+, K~+, Na~+, Rb~+, Cs~+; M~+= Ag. Al, Cd, Co. Cr, Cu. Fe. Ga 'in Mn, Ni. Pb; M" = Cr, Fe, Mn). as determined by solidtate voltammetric experiments. The experimental data can be nderstood both in terms of the polarizing effect (ionic potential) of the nitrogen-bonded M'~(n+) ions and also in terms of the free energy of hydration of the cations M~+, which are inserted into the channels and holes of the zeolitic structure of the solid -compounds during reduction of the [M"(CN)_6]~(m-) units of the solid compounds. The results of this study support the assumption that M"→C π back bonding increases as the acid-base interactionon the nitrogen end of the cyanide ions increases.