在Fe(II) 旋转交叉复合体中,光诱导的旋转状态切换与基于 thiazole 的合联体发生交叉
Minyoung Jo1, Botagoz Amanyazova1,2, Sandugash Yergeshbayeva1
1Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, USA. shatruk@chem.fsu.edu.
Dalton transactions (Cambridge, England : 2003)
|June 6, 2024
概括
铁 (II) 复合物与基于 thiazole 的配体表现出可调节的旋转交叉行为. 在这些材料中,更强的分子间相互作用促进了合作性旋转过渡和光诱导激发的旋转状态捕获 (LIESST).
科学领域:
- 协调化学 协调化学
- 材料科学 材料科学 材料科学
- 固态物理 固态物理
背景情况:
- 铁 (II) 复合体中的旋转交叉 (SCO) 是一种在分子开关和传感器中具有潜在应用的现象.
- 基于 thiazole 的连接物为设计 SCO 材料提供可调节的电子和硬质性质.
- 了解晶体包装和分子间相互作用对SCO行为的影响对于材料设计至关重要.
研究的目的:
- 合成和表征新型同质 iron (II) 复合物与基于 thiazole 的双酸联体.
- 为了研究这些复合物的旋转交叉特性和晶体结构.
- 为了探索光诱导激发自旋状态捕获 (LIESST) 现象和放松动态.
主要方法:
- 铁复合物的合成与4,4'-bithiazole (4bt),2,2'-bithiazole (2bt) 和3-(thiazol-2-yl) pyrazole (3tpH) 连接物.
- 测定X射线晶体结构以分析晶体包装和分子间相互作用.
- 可变温度磁感应度测量以研究旋转交叉过渡.
- 光学吸收光谱检查LIESST和放松动态.
主要成果:
- 成功合成了三种同质铁 (II) 复合物,即[Fe4bt]3,[FeClO4]2 (1),[Fe2bt]3,[ClO4]2 (2) 和[Fe3tpH]3,[ClO4]2 (3) 的合成.
- 晶体结构显示出不同的分子间相互作用,在2·MeOH和3·2(3tpH) 复合体中相互作用更强烈.
- 复合体2和3·2(3tpH) 在235K和159K分别表现出合作旋转过渡,并显示了LIESST行为.
- 综合体1显示由于较弱的相互作用,旋转交叉在300K以上逐渐发生.
- LIESST状态的放松动态在3·2(3tpH) 中表明了合作效应和复杂的放松机制.
结论:
- 铁 (II) 复合体的旋转交叉行为和 LIESST 特性受到连接体选择和晶体包装的强烈影响.
- 由特定的分子间相互作用产生的合作效应在上海合作组织和放松动态中发挥着重要作用.
- 这些发现为具有可切换性质的分子材料的合理设计提供了洞察力.
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