Regueiro A, Castells-Gil J, Shen C, Mikulska I, Allen C, Bogani L, Torres-Cavanillas R
Instituto de Ciencia Molecular, Universitat de València Catedrático José Beltrán 2 46980 Paterna Spain
School of Chemistry, University of Birmingham Birmingham B15 2TT UK.
Mater Adv. 2024 Aug 31;5(18):7473-7480. doi: 10.1039/d4ma00262h. eCollection 2024 Sep 16.
The induction of structural distortion in a controlled manner through tilt engineering has emerged as a potent method to finely tune the physical characteristics of Prussian blue analogues. Notably, this distortion can be chemically induced by filling their pores with cations that can interact with the cyanide ligands. With this objective in mind, we optimized the synthetic protocol to produce the stimuli-responsive Prussian blue analogue A Mn[Fe(CN)] with A = K, Rb, and Cs, to tune its stimuli-responsive behavior by exchanging the cation inside pores. Our crystallographic analyses reveal that the smaller the cation, the more pronounced the structural distortion, with a notable 20-degree Fe-CN tilting when filling the cavities with K, 10 degrees with Rb, and 2 degrees with Cs. Moreover, this controlled distortion offers a means to switch on/off its stimuli-responsive behavior, while modifying its magnetic response. Thereby empowering the manipulation of the PBA's physical properties through cationic exchange.
通过倾斜工程以可控方式诱导结构畸变已成为一种微调普鲁士蓝类似物物理特性的有效方法。值得注意的是，这种畸变可通过用能与氰化物配体相互作用的阳离子填充其孔隙来化学诱导。出于这一目的，我们优化了合成方案，以制备具有刺激响应性的普鲁士蓝类似物A Mn[Fe(CN)]，其中A = K、Rb和Cs，并通过交换孔隙内的阳离子来调节其刺激响应行为。我们的晶体学分析表明，阳离子越小，结构畸变越明显，用K填充空腔时Fe-CN倾斜明显达20度，用Rb时为10度，用Cs时为2度。此外，这种可控畸变提供了一种开启/关闭其刺激响应行为的方法，同时改变其磁响应。从而通过阳离子交换实现对PBA物理性质的操控。
