6533b851fe1ef96bd12aa22e

RESEARCH PRODUCT

Pressure-induced electron transfer in ferrimagnetic Prussian blue analogs

subject

description

M\"ossbauer and magnetic susceptibility measurements were performed under pressure on three Prussian blue analogs, ${\mathrm{K}}_{0.1}{\mathrm{Co}}_{4}[{\mathrm{Fe}(\mathrm{CN})}_{6}{]}_{2.7}\ensuremath{\cdot}18{\mathrm{H}}_{2}\mathrm{O},$ ${\mathrm{K}}_{0.28}{\mathrm{Co}}_{4}[{\mathrm{Fe}(\mathrm{CN})}_{6}{]}_{2.76}\ensuremath{\cdot}18{\mathrm{H}}_{2}\mathrm{O},$ and ${\mathrm{Cs}}_{0.7}{\mathrm{Co}}_{4}[{\mathrm{Fe}(\mathrm{CN})}_{6}{]}_{2.9}\ensuremath{\cdot}16{\mathrm{H}}_{2}\mathrm{O}.$ A pressure-induced electron transfer ${\mathrm{Co}}^{2+}(S=\frac{3}{2})\ensuremath{-}{\mathrm{Fe}}^{3+}(S=\frac{1}{2})\ensuremath{\rightarrow}{\mathrm{Co}}^{3+}(S=0)\ensuremath{-}{\mathrm{Fe}}^{2+}(S=0)$ was found. The ``scanning'' of the ligand field strength by applying an external hydrostatic pressure allows the exploration of the distribution of ${\mathrm{CoN}}_{n}{\mathrm{O}}_{6\ensuremath{-}n}(0l~nl~6)$ configurations. It reveals a narrow distribution of configurations centered around the most probable ${\mathrm{CoN}}_{4}{\mathrm{O}}_{2}$ configuration in ${\mathrm{K}}_{0.1}{\mathrm{Co}}_{4}[{\mathrm{Fe}(\mathrm{CN})}_{6}{]}_{2.7}\ensuremath{\cdot}18{\mathrm{H}}_{2}\mathrm{O}$ and a broad ${\mathrm{CoN}}_{n}{\mathrm{O}}_{6\ensuremath{-}n}$ distribution in ${\mathrm{K}}_{0.28}{\mathrm{Co}}_{4}[{\mathrm{Fe}(\mathrm{CN})}_{6}{]}_{2.76}\ensuremath{\cdot}18{\mathrm{H}}_{2}\mathrm{O}$ and ${\mathrm{Cs}}_{0.7}{\mathrm{Co}}_{4}[{\mathrm{Fe}(\mathrm{CN})}_{6}{]}_{2.9}\ensuremath{\cdot}16{\mathrm{H}}_{2}\mathrm{O}.$ This evolution of site distribution caused by alkali doping, explored here for the first time, to our knowledge is shown to play an important role in the photoinduced magnetization process.