在电离框架中可编程的反交叉行为
Si-Guo Wu1, Long-Fei Wang1, Ze-Yu Ruan1
1Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education, School of Chemistry, Sun Yat-Sen University, 510275 Guangzhou, Guangdong, P. R. China.
Journal of the American Chemical Society
|August 2, 2022
概括
这项研究介绍了一种新金属有机框架 (MOF),表现出可切换的旋转交叉 (SCO) 行为. 化学氧化还原反应可以精确控制多步SCO动态,为先进的分子开关铺平道路.
科学领域:
- 材料科学
- 无机化学
- 超分子化学
背景情况:
- 金属有机框架 (MOF) 是创造多响应材料的多功能平台.
- 旋转交叉 (SCO) 材料表现出基于外部刺激的可调节磁性.
研究的目的:
- 合成一种具有歇斯底里的旋转交叉行为的新型阴离子MOF.
- 调查MOF用于操纵SCO动态的氧化还原可编程能力.
- 探索MOF作为多响应分子开关的潜力.
主要方法:
- 合成含有中性四联体和二氨酸的阴离子MOF.
- 通过氧化黄金 (I) 到黄金 (III) 中心进行合成后的改性.
- 使用L-ascorbic酸进行氧化处理以改变SCO行为.
- 周期密度函数理论 (DFT) 计算以合理化实验观测.
主要成果:
- 合成了一种罕见的化MOF,FeII{TPB}{AuI{CN}2}I·4H2O·4DMF,呈现室温附近的歇斯底里性SCO.
- MOF显示了对二素分子的氧化还原可编程反应.
- 氧化Au (I) 连接器导致从单阶段转换为双阶段 (Br2) 或三阶段 (I2) 歇斯底里SCO.
- 通过l-ascorbic酸的减少成功地将SCO行为恢复为单步过程.
结论:
- 这项工作展示了由化学氧化还原反应控制的可切换一/二/三步SCO动态的第一个实例.
- 开发的MOF为设计具有可调节动态的多响应分子开关提供了一个新的平台.
- 这些发现在响应材料和分子电子领域开辟了新的视角.
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