Probing the Influence of Defects, Hydration, and Composition on Prussian Blue Analogues with Pressure

The vast compositional space of Prussian blue analogues (PBAs), formula AM[M'(CN)₆]·nH₂O, allows for a diverse range of functionality. Yet, the interplay between composition and physical properties-e.g., flexibility and propensity for phase transitions-is still largely unknown, despite its fundamental and industrial relevance. Here we use variable-pressure X-ray and neutron diffraction to explore how key structural features, i.e., defects, hydration, and composition, influence the compressibility and phase behavior of PBAs. Defects enhance the flexibility, manifesting as a remarkably low bulk modulus (B₀ ≈ 6 GPa) for defective PBAs. Interstitial water increases B₀ and enables a pressure-induced phase transition in defective systems. Conversely, hydration does not alter the compressibility of stoichiometric MnPt(CN)₆, but changes the high-pressure phase transitions, suggesting an interplay between low-energy distortions. AMnCo(CN)₆ (A^I = Rb, Cs) transition from F4̅3m to P4̅n2 upon compression due to octahedral tilting, and the critical pressure can be tuned by the A-site cation. At 1 GPa, the symmetry of Rb_0.87Mn[Co(CN)₆]_0.91 is further lowered to the polar space group Pn by an improper ferroelectric mechanism. These fundamental insights aim to facilitate the rational design of PBAs for applications within a wide range of fields.