Tailorable Topologies for Selectively Controlling Crystals of Expanded Prussian Blue Analogs

Chemical manipulations of Prussian blues and Prussian blue analogues (PBAs) beyond first-row transition-metal cations have remained quite preliminary to this day. The presented report demonstrates the feasibility of using different types of cations, including general transition-metal ions, p region elements in the periodic table, lanthanide elements, and overlooked cations such as Al3+ and Mo3+ to build unique PBAs. A systematic study of the different types of PBAs is provided in terms of physical and chemical features by means of transition electron microscopy, X-ray photoelectron spectroscopy, and X-ray absorption near-edge structure. Diverse PBAs can be synthesized with different morphologies. The [Ni(CN)4]2–-based PBAs mainly exhibited layered products owing to their 4-fold-coordinated anions. The 6-fold-coordinated anion-based PBAs displayed cubic or distorted cubic crystal structures following the same method of ion arrangements with conventional [Fe(CN)6]2-/3–-based PBAs. Furthermore, bonding condi...