<br>具有 90 K 范围内可调转变温度的二维自旋交叉分子固溶体,Journal of the American Chemical Society

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具有 90 K 范围内可调转变温度的二维自旋交叉分子固溶体
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2024-02-27 , DOI: 10.1021/jacs.3c12905
Ying-Ying Wu ₁ , Zhao-Yang Li ₁ , Shuang Peng ₁ , Zi-Yi Zhang ₁ , Hao-Ming Cheng ₁ , Hang Su ₁ , Wen-Qi Hou ₁ , Feng-Lei Yang ₂ , Shu-Qi Wu ₃ , Osamu Sato ₃ , Jing-Wei Dai ₄ , Wei Li ₁ , Xian-He Bu ₁

Affiliation

自旋交叉（SCO）材料作为分子器件中的双稳态开关表现出巨大的潜力。然而，已知化合物的自旋转变温度（ T _c ）无法覆盖整个环境温度范围，很大程度上限制了它们的实际用途。本研究报道了一个示例性的二维SCO固溶体体系， [Fe ^III (H _0.5 L ^Cl ) _{2 – 2 x} (H _0.5 L ^F ) _{2 x} ]·H ₂ O (H _0.5 L ^X = 5- X -2 -羟基亚苄基肼硫甲酰胺， X =F或Cl， x =0至1)，其中相邻层通过氢键粘合。值得注意的是，该系统的T _c可以通过调节L ^F配体的分数x以线性方式在 90 K (227–316 K) 范围内进行微调。提高x会增强相邻层之间的氢键，从而增强相邻 SCO 分子之间的分子间相互作用。单晶衍射分析和周期密度泛函理论计算表明，这种特殊的层间相互作用的改变增强了Fe ^III N ₂ O ₂ S ₂配体场和相应的SCO能垒，从而导致T _c增加。这项工作为通过分子相互作用的精细操控来调节 SCO 材料的T _c提供了一条新途径，这可以将双稳态分子固体的应用扩展到更广泛的温度范围。

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Two-Dimensional Spin-Crossover Molecular Solid Solutions with Tunable Transition Temperatures across 90 K

Spin-crossover (SCO) materials exhibit remarkable potential as bistable switches in molecular devices. However, the spin transition temperatures (T_c) of known compounds are unable to cover the entire ambient temperature spectrum, largely limiting their practical utility. This study reports an exemplary two-dimensional SCO solid solution system, [Fe^III(H_0.5L^Cl)_2–2x(H_0.5L^F)_2x]·H₂O (H_0.5L^X = 5-X-2-hydroxybenzylidene-hydrazinecarbothioamide, X = F or Cl, x = 0 to 1), in which the adjacent layers are adhered via hydrogen bonding. Notably, the T_c of this system can be fine-tuned across 90 K (227–316 K) in a linear manner by modulating the fraction x of the L^F ligand. Elevating x results in strengthened hydrogen bonding between adjacent layers, which leads to enhanced intermolecular interactions between adjacent SCO molecules. Single-crystal diffraction analysis and periodic density functional theory calculations revealed that such a special kind of alteration in interlayer interactions strengthens the Fe^IIIN₂O₂S₂ ligand field and corresponding SCO energy barrier, consequently resulting in increased T_c. This work provides a new pathway for tuning the T_c of SCO materials through delicate manipulation of molecular interactions, which could expand the application of bistable molecular solids to a much wider temperature regime.

更新日期：2024-02-27

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