Li Kai, Hu Shuxian, Zou Qing, Zhang Yugang, Zhang Hailong, Zhao Yuan, Zhou Tong, Chai Zhifang, Wang Yaxing
State Key Laboratory of Radiation Medicine and Protection, School for Radiological and Interdisciplinary Sciences and Collaborative Innovation Center of Radiation Medicine of Jiangsu Higher Education Institutions, Soochow University, Suzhou 215123, P. R. China.
Beijing Computational Science Research Center, Beijing 100193, P. R. China.
Inorg Chem. 2021 Jun 21;60(12):8984-8989. doi: 10.1021/acs.inorgchem.1c00886. Epub 2021 May 28.
We report the synthesis, single-crystal structure, solid-state ultraviolet-visible-near-infrared spectroscopy, and theoretical calculations on the first trivalent plutonium crown ether inclusion complex, [(HO)(18-crown-6)]Pu(HO)(18-crown-6)·2(HO) (denoted as Pu-18C6). Single-crystal X-ray diffraction reveals that Pu-18C6 crystallizes in the orthorhombic space group of , which is assembled by independent ionic pairs including [Pu(HO)(18-crown-6)], [(HO)(18-crown-6)], and perchlorate anions. The plutonium atom is fully encapsulated within the cavity of the 18-crown-6, generating a distorted bicapped square antiprism geometry. The theoretical evaluation confirms that weak Pu-O dative bond is involved between Pu ions with 18-crown-6. This work may deepen the understanding of the host-guest interactions between trivalent transuranic and macrocyclic ligands.
我们报道了首例三价钚冠醚包合物[(HO)(18-冠-6)]Pu(HO)(18-冠-6)·2(HO)（记为Pu-18C6）的合成、单晶结构、固态紫外-可见-近红外光谱及理论计算。单晶X射线衍射表明，Pu-18C6结晶于正交空间群，由包括[Pu(HO)(18-冠-6)]、[(HO)(18-冠-6)]和高氯酸根阴离子的独立离子对组装而成。钚原子完全被包裹在18-冠-6的腔内，形成扭曲的双帽四方反棱柱几何构型。理论评估证实，钚离子与18-冠-6之间存在弱的钚-氧配位键。这项工作可能会加深对三价超铀元素与大环配体之间主客体相互作用的理解。
