Metal-to-Metal Electron Transfer in Co/Fe Prussian Blue Molecular Analogues: The Ultimate Miniaturization

Co/Fe Prussian Blue analogues are known to display both thermally and light induced electron transfer attributed to the switching between diamagnetic {Fe^II_LS(μ‑CN)­Co^III_LS} and paramagnetic {Fe^III_LS(μ‑CN)­Co^II_HS} pairs (LS = low spin; HS = high spin). In this work, a dinuclear cyanido-bridged Co/Fe complex, the smallest {Fe­(μ‑CN)­Co} moiety at the origin of the remarkable physical properties of these systems, has been designed by a rational building-block approach. Combined structural, spectroscopic, magnetic and photomagnetic studies reveal that a metal-to-metal electron transfer that can be triggered in solid state by light, temperature and solvent contents, is observed for the first time in a dinuclear complex.