Effect of supporting electrolytes on the positions of outer-sphere charge-transfer bands in electronic absorption spectra

doi:10.1070/MC2001v011n03ABEH001441

Mendeleev Communications

Volume 11, Issue 3, 2001, Pages 88-89

https://doi.org/10.1070/MC2001v011n03ABEH001441 Get rights and content

The positions of the outer-sphere charge-transfer bands in the electronic absorption spectra of the EV²⁺–[Fe(CN)₆]^4– system depend on the nature and concentration of supporting-electrolyte cations.

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Cited by (2)

Dihydrohexacyanoferrates of N-heterocyclic cations
2007, Inorganica Chimica Acta
Dihydrohexacyanoferrates (II and III) of aromatic N-heterocyclic cations X⁺ (such as N-methylquinoxalinium, pyridinium, dipyridinium) and X²⁺ (such as pyridylpyridinium, dipyridinium) are synthesized and characterized. For the first time, the crystal structures of acidic dihydrohexacyanoferrates are described. The formation of the $X_{2}^{+} H_{2} [Fe (CN)_{6}]$ and X²⁺H₂[Fe(CN)₆] species which contain the [Fe(CN)₆]⁴⁻ and [Fe(CN)₄(CNH)₂]²⁻ anions from acidic solutions occurs after the formation of the H[Fe(CN)₆]³⁻ species as can be established from the outer-sphere charge transfer (OSCT) bands in the absorption spectra. The crystal structures of these species contain extensive network of intermolecular N–H⋯N, N–H⋯O and O–H⋯N hydrogen bonds which link the hexacyanoferrate anions with solvent water (if present) and N-heterocyclic cations if the later can participate in the H-bond formation. In the crystals of dihydrohexacyanoferrates, the H-bond networks can be two-dimensional (species 1) and three-dimensional (species 2–7). The lack of acidic protons for the H-bond network formation can be compensated by solvent water molecules. The H-bond network plays an important role in stabilization of such strongly-acidic species such as the H₂Bpy²⁺ and HPypy²⁺ cations and the [Fe^II(CN)₄(CNH)₂]²⁻ anion.
Outer-sphere charge transfer between the hexacyanoferrate anion and the Dq<sup>2+</sup> cation
2005, Russian Journal of Inorganic Chemistry

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Effect of supporting electrolytes on the positions of outer-sphere charge-transfer bands in electronic absorption spectra

J. Electroanal. Chem.

Mendeleev Commun.

Chem. Phys. Lett.

Inorg. Chem.

Can. J. Chem.

J. Phys. Chem.