Incorporation of Cyano Transition Metal Complexes in KCl Crystals—Experimental and Computational Studies

Abstract

Experimental and computational studies of the incorporation of hexacyanoferrate(II), hexacyanocobaltate(III), and hexacyanoferrate(III) into potassium chloride crystals are described. The experimental results showed that the extent of incorporation follows the trend hexacyanoferrate(II) » hexacyanoferrate(III) > hexacyanocobaltate(III). Computational modelling produced replacement energies that match the experimental trend. The calculated geometry of the incorporated complexes was also found to match well with previous experimental results.

Solid‐State Redox Solutions: Microfabrication and Electrochemistry

“…Owing to the similar lattice structures, the transition metal cyanide complexes (such as Fe, Co, Ni, Rh, Ir, Pt, Pt) can also form solid-state redox solution in NaCl, KCl, or AgCl crystals. [11][12][13][14][21][22][23][24][25][26][27][28] As another example, the solid-state solution of Co(CN) 6 3À in a NaCl microcrystal fabricated through this technique is shown in the Supporting Information, S4. These kinds of solid-state solution usually preserve some specific properties, such as electric conductivity and luminescent and electrochemical properties, which are not found in their aqueous solutions.…”

Heterogeneous versus homogeneous electron transfer reactions at liquid–liquid interfaces: The wrong question?

“…We also need to consider the size and the orientation of the precursor <D|A>. The crystallographic radii of Fc and [Fe(CN)6] 3are 0.33-0.365 nm [60,61] and 0.475 nm (computational crystallographic radius, [62]), respectively, so the precursor spans over this extremely thin interface. Another question is then, what is the closest approach for the different species to the interface.…”

Dielectric-dependent electron transfer behaviour of cobalt hexacyanides in a solid solution of sodium chloride

“…Since the lattice size of Na 3 Co(CN) 6 (9.39 Å) is very close to that of NaCl (9.2 Å), this means that the Co(CN) 6 3– units can take the place of the NaCl 6 5– units and dope into the NaCl microcrystal to form a solid solution. 11 , 12 As the valence of the Co 3+ is higher than the Na + , to achieve electroneutrality, two Na + vacancies are left in the neighboring NaCl 6 5– units. That means the Na 3 Co(CN) 6 /NaCl solid solution is a Na + ionic conductor.…”