Controlled Light and Temperature Induced Valence Tautomerism in a Cobalt-o-Dioxolene Complex.
Controlled Light and Temperature Induced Valence Tautomerism in a Cobalt-o-Dioxolene Complex.
复制标题
受控光和温度诱导钴邻二氧杂环戊烯配合物中的价态互变异构。
DOI：
10.1021/acs.inorgchem.1c00638
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发表时间：
2021
影响因子：
4.6
通讯作者：
Leroy L
中科院分区：
文献类型：
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作者：
Leroy L
3，5-二叔丁基儿茶酚盐和氰基吡啶的单核钴配合物（Co（diox）2（4-CN-py）2）是一种非常通用的化合物，其在固态下显示出价态互变异构（VT），其受温度、光和硬X射线诱导，并受晶格中的溶剂调制。在我们的工作中，我们使用单晶X射线衍射作为固态光致VT的探针，并证明通过衰减控制使用硬X射线，以避免X射线诱导的VT相互转换。报道了Co（diox）2（4-CN-py）2苯溶剂化晶体在30 K下用450 nm蓝光照射时的光诱导VT，得到了非常高的亚稳hs-Co Ⅱ态产率（80%），并且我们还证明了用660 nm红光照射时这些光诱导亚稳态的去激发。这种高产率的光诱导VT从未在钴互变异构体的分子晶体中实验观察到，证明450 nm的光照射引发了导致thels-Co IIItohs-Co II互变的事件链。
The mononuclear cobalt complex of 3,5-di-tert-butylcathecolate and cyan-pyridine (Co(diox)2(4-CN-py)2) is a very versatile compound that displays valence tautomerism (VT) in the solid state, which is induced by temperature, light, and hard X-rays, and modulated by solvent in the crystal lattice. In our work, we used single crystal X-ray diffraction as a probe for the light-induced VT in solid state and demonstrate the controlled use of hard X-rays via attenuation to avoid X-ray-induced VT interconversion. We report photoinduced VT in benzene solvated crystals of Co(diox)2(4-CN-py)2illuminated with blue 450 nm light at 30 K with a very high yield (80%) of metastablehs-CoIIstates, and we also show evidence of the de-excitation of these photoinduced metastable states using red 660 nm light. Such high-yield light-induced VT had never been experimentally observed in molecular crystals of cobalt tautomers, proving that the 450 nm light illumination is triggering a chain of events that leads to thels-CoIIItohs-CoIIinterconversion.