Mixed Orbital Ground States of Fe2+ in Prussian Blues

We report on the mixed-orbital ground state compounds analogous to the mixed-valence ones. Orbital doublet and singlet ground states of the Fe2+ ion displayed in Moessbauer spectra of the Prussian blue analogues AyFe3-y[Co(CN)6]2xH2O (y<1) are interconverting to each other as temperature changes for A = K, Na. Relative weight of orbital singlet ground states increases with lowering temperature. In the alcali-free cobalticyanides, the Moessbauer spectra are dominated by quadrupole-splt doublets of the same origin with a large splitting characteristic of the Fe2+ species coordinated by two (at least) oxygen atoms of water molecules in cis-configuration. Single type octahedral coordination of Fe2+ is isolated in A-filled cobalticyanides for A=Rb, Cs to be characterized by the narrower quadrupole spectrum associated with the orbital doublet ground states. Ionic exchange of K for Cs in KFe[Co(CN)6]H2O results in predominance of the orbital singlet, i.e., in enhanced anisotropy of the Fe2+ valence electrons. We found hence that the Fe2+ charge distribution can be modified together with crystal size at the step of synthesis owing to distortion isomerism.