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. 2021 Mar 10;143(9):3544-3554.
doi: 10.1021/jacs.0c13181. Epub 2021 Feb 25.

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

Hanna L B Boström  1   2   3 , Ines E Collings  4 , Dominik Daisenberger  5 , Christopher J Ridley  6 , Nicholas P Funnell  6 , Andrew B Cairns  7   8
Affiliations

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

Hanna L B Boström et al. J Am Chem Soc. .

Abstract

The vast compositional space of Prussian blue analogues (PBAs), formula AxM[M'(CN)6]y·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 (AI = 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 Rb0.87Mn[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.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Different classes of Prussian blue analogues: defective M[M′(CN)6]y<1·nH2O, stoichiometric MM′(CN)6·nH2O and alkali-metal-containing AxM[M′(CN)6]y. The lower panel shows the systems investigated in this study.
Figure 2
Figure 2
Background-subtracted XRD patterns of (a) MnPt and (b) MnPt·nH2O at 0 and 1.4 GPa. Data for MnPt·nH2O were reported in ref (23).
Figure 3
Figure 3
(a) The percentage change in the unit cell volume of defective and stoichiometric PBAs. (b) The cell volume as a function of pressure for MnPt and Mn[Co]0.67. Empty symbols are used for defective systems and hydrated compounds are denoted with blue markers. Errors in y are smaller than the data markers and pressure errors are within 0.1 GPa.
Figure 4
Figure 4
Crystal structures of the tetragonal and monoclinic high-pressure phases of RbMnCo. The structures are rotated to ensure a consistent viewing direction.
Figure 5
Figure 5
Pressure dependence of the strut lengths rab and rc for (a) RbMnCo and (b) CsMnCo and of (c) the hinging angle ϕ for RbMnCo. The transition pressures are denoted by vertical dashed lines or a gray rectangle. (d) The parametrization of the PBA structure in terms of the mechanical building units.
Figure 6
Figure 6
(a) The pressure–composition phase diagram of the Prussian blue analogues studied here. The hashed bar for MnPt corresponds to an unsolved phase. (b) The bulk moduli of the ambient phases as a function of composition. Note that the bulk modulus of RbMnCo is calculated based on two data points and should be interpreted with caution.
See this image and copyright information in PMC

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