在金属-有机框架中的铁的高旋转状态的压力诱导意外稳定
Livia Getzner1, Yasmine Remili1, Damian Paliwoda1
1LCC, CNRS and Université de Toulouse, UPS, INP, Toulouse 31077, France.
Journal of the American Chemical Society
|December 3, 2025
概括
水静压会导致金属有机结构中的异常旋转状态转变. 这种自旋交叉现象是可逆的,与电子转移和结构变化有关.
科学领域:
- 材料科学
- 协调化学
- 超分子化学
背景情况:
- 旋转交叉 (SCO) 材料显示高旋转 (HS) 和低旋转 (LS) 状态之间的切换.
- 金属有机框架 (MOF) 为探索SCO现象提供了可调的结构.
- 压力是诱导和控制旋转转变的关键参数.
研究的目的:
- 研究水静压对特定铁基MOF的旋转状态的影响.
- 确定压力诱导的旋转状态转换及其可逆性.
- 阐明基础结构变化和电子转移机制.
主要方法:
- 拉曼光谱检测旋转状态.
- 在高压下单晶X射线衍射 (SC-XRD) 分析结构变化.
- 铁基金属有机框架的合成和特征.
主要成果:
- 1.2 GPa 的水静压诱导了高旋转 (S=2) 到低旋转 (S=0) 的转变.
- 意外地,压力增加到2.0GPa导致可逆回归到高旋转状态.
- 进一步增加压力至2.5GPa,导致再次回到低旋转状态.
- 高压SC-XRD揭示了与电子转移相关的并发结构变化,包括金属连接体延长和晶格收缩.
结论:
- 研究的MOF表现出一种不寻常的,可逆的压力驱动的旋转状态转换序列.
- 在这些转换中,氧化还原活性联体之间的电子转移起着至关重要的作用.
- 观察到的现象挑战了旋转交叉行为的经典热力学预测.
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