Theoretical Insights into Preorganized Pyridylpyrazole-Based Ligands toward the Separation of Am(III)/Eu(III)

doi:10.1021/acs.inorgchem.8b02550

	Theoretical Insights into Preorganized Pyridylpyrazole-Based Ligands toward the Separation of Am(III)/Eu(III)
	Lan JH(蓝建慧); Wu QY(吴群燕); Kong XH(孔祥鹤); Chai, Z. F.; Wang, C. Z.; Lan, J. H.; Wu, Q. Y.; Kong, X. H.; Shi WQ(石伟群); Chai ZF(柴之芳)
刊名	INORGANIC CHEMISTRY
	2018
卷号	57 期号:23 页码:14810-14820
ISSN号	0020-1669
DOI	10.1021/acs.inorgchem.8b02550
文献子类	Article
英文摘要	Pyridylpyrazole ligands have shown excellent competence for partitioning actinides from lanthanides. As far as we know, the preorganization structure of the ligand has a great impact on the extraction separation ability. However, the mechanism that works well for some ligands but fails for others needs to be clearly elucidated. In this work, we designed three various pyridylpyrazole ligands, BPP, BPBP, and BPPhen, and further preorganized one or both side pyrazole rings of these ligands. The properties of these ligands and the coordination structures, bonding nature and thermodynamic behaviors of the related Am(III) and Eu(III) complexes have been systematically studied in a theoretical fashion. All analyses of geometries, charge transfer, QTAIM (quantum theory of atoms in molecules) and NBO (natural bond orbital) suggest that the Am N bonds possess more covalence compared to that of Eu N bonds. According to the thermodynamic results, increasing the rigidity of the bridging skeleton rather than the side chain can enhance the extraction ability and Am(III)/Eu(III) selectivity of the ligand. This work may identify the reasonability of a useful approach on achieving highly efficient Am(III)/Eu(III) separation through tuning the preorganization level of the ligand and further provide meaningful theoretical basis on the input of preorganization toward ligand design and screening.
电子版国际标准刊号	1520-510X
WOS关键词	ENERGY-ADJUSTED PSEUDOPOTENTIALS ; SEGMENTED CONTRACTION SCHEME ; ELECTRONIC-STRUCTURE ; SELECTIVE EXTRACTION ; SOLVENT-EXTRACTION ; COMPLEXES ; ACTINIDE ; DENSITY ; EU(III) ; LANTHANIDE
WOS研究方向	Chemistry
语种	英语
WOS记录号	WOS:000452344400041
内容类型	期刊论文
源URL	[http://ir.ihep.ac.cn/handle/311005/286865]
专题	高能物理研究所_多学科研究中心
通讯作者	Shi WQ(石伟群)
作者单位	中国科学院高能物理研究所
推荐引用方式 GB/T 7714	Lan JH,Wu QY,Kong XH,et al. Theoretical Insights into Preorganized Pyridylpyrazole-Based Ligands toward the Separation of Am(III)/Eu(III)[J]. INORGANIC CHEMISTRY,2018,57(23):14810-14820.
APA	蓝建慧.,吴群燕.,孔祥鹤.,Chai, Z. F..,Wang, C. Z..,...&Nie, C. M..(2018).Theoretical Insights into Preorganized Pyridylpyrazole-Based Ligands toward the Separation of Am(III)/Eu(III).INORGANIC CHEMISTRY,57(23),14810-14820.
MLA	蓝建慧,et al."Theoretical Insights into Preorganized Pyridylpyrazole-Based Ligands toward the Separation of Am(III)/Eu(III)".INORGANIC CHEMISTRY 57.23(2018):14810-14820.