Prussian blue analogues (PBAs) are a highly tunable family of materials with properties suitable for a wide variety of applications. Although their straightforward aqueous synthesis allows for the facile preparation of a diverse set of compositions, the use of water as the solvent has hindered the preparation of specific compositions with highly sought-after properties. A typical example is Cr[Cr(CN)₆]: its predicted strong magnetic interactions have motivated many attempts at its synthesis but with limited success. The lack of control over vacancies, crystallinity, and the oxidation state has prevented the experimental validation of its theoretical magnetic properties. Here, we report the nonaqueous synthesis of vacancy-suppressed, nanocrystalline chromium hexacyanochromate. The control over vacancies and the oxidation state leads to stronger magnetic interactions with a markedly increased absolute Weiss temperature (Θ = −836(6) K) and magnetic ordering temperature of (240 ± 10) K. Our results challenge the notion of the solvent as merely reaction medium and introduce a pathway for exploring moisture- and air-sensitive PBA compositions.

中文翻译：

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低空位六氰基铬酸盐的非水合成


普鲁士蓝类似物 （PBA） 是一系列高度可调的材料，其特性适用于各种应用。尽管它们简单的水合成允许轻松制备多种组合物，但使用水作为溶剂阻碍了具有备受追捧特性的特定组合物的制备。一个典型的例子是 Cr[Cr（CN）₆]：它预测的强磁相互作用激发了许多合成它的尝试，但成功率有限。缺乏对空位、结晶度和氧化态的控制阻碍了对其理论磁特性的实验验证。在这里，我们报道了空位抑制的纳米晶六氰基铬酸盐的非水合成。对空位和氧化态的控制导致更强的磁相互作用，绝对 Weiss 温度 （Θ = −836（6） K） 和 （240 ± 10） K 的磁排序温度显着升高。我们的结果挑战了溶剂仅作为反应介质的概念，并为探索对水分和空气敏感的 PBA 组成引入了一条途径。