Influence of denticity and combined soft-hard strategy on the interaction of picolinic-type ligands with NpO2+

doi:10.1039/c6ra26114k

	Influence of denticity and combined soft-hard strategy on the interaction of picolinic-type ligands with NpO2+
	Chai ZF(柴之芳); Ling HC(凌鸿财); Chai, ZF; Wang, DQ; Xia, MR; Ling, HC; Wang DQ(王东琪); Chen, WK; Xia MR(夏苗仁)
刊名	RSC ADVANCES
	2017
卷号	7 期号:20 页码:12236-12246
ISSN号	2046-2069
DOI	10.1039/c6ra26114k
文献子类	Article
英文摘要	The interaction of neptunyl ions (NpO2+) with three picolinic type ligands (L), including the deprotonated picolinic acid anion (PA(-)), the deprotonated dipicolinic acid anion (DPA(2-)) and the 1,10-phenanthroline2,9-dicarboxylic acid anion (PADA(2-)), was investigated by using a density functional theory method with various stoichiometric ratios of Np : L = 1 : 1, 1 : 2, and 1 : 3. The coordination modes, the influence of the denticity of the ligands, and the stoichiometry of the complexes were evaluated in terms of geometry, electronic structure, and thermodynamics. The calculations show that the coordination of NpO2+ to tetradentate ligands is more stable than that to tridentate and bidentate ones, and the coordination ability of the three deprotonated ligands follows the order: PADA(2-) > DPA(2-) > PA(-). Quantum theory of atoms-in-molecules (QTAIM) analysis, charge decomposition analysis (CDA) and natural atomic orbital (NAO) analysis were used to understand the bonding nature and electronic properties of the complexes, and the metal-ligand dative bond was identified to be mainly ionic. In view of the favorable coordination modes and the distinct ability of the ligands in binding to neptunyl, we conclude that the denticity of the ligands and the combined hard-soft donor strategy work cooperatively in the coordination of NpO2+ with ligands. This work is expected to contribute to the rational design of new types of ligand with enhanced ability to extract neptunyl.
WOS关键词	CHARGE DECOMPOSITION ANALYSIS ; DENSITY-FUNCTIONAL THEORY ; HIGHLY EXCITED MOLECULES ; SPENT NUCLEAR-FUEL ; BASIS-SETS ; GAS-PHASE ; ELECTRONIC-STRUCTURE ; ENERGY-TRANSFER ; DONOR LIGANDS ; COMPLEXES
WOS研究方向	Chemistry
语种	英语
WOS记录号	WOS:000395873500051
内容类型	期刊论文
源URL	[http://ir.ihep.ac.cn/handle/311005/285180]
专题	高能物理研究所_多学科研究中心
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	Chai ZF,Ling HC,Chai, ZF,et al. Influence of denticity and combined soft-hard strategy on the interaction of picolinic-type ligands with NpO2+[J]. RSC ADVANCES,2017,7(20):12236-12246.
APA	柴之芳.,凌鸿财.,Chai, ZF.,Wang, DQ.,Xia, MR.,...&夏苗仁.(2017).Influence of denticity and combined soft-hard strategy on the interaction of picolinic-type ligands with NpO2+.RSC ADVANCES,7(20),12236-12246.
MLA	柴之芳,et al."Influence of denticity and combined soft-hard strategy on the interaction of picolinic-type ligands with NpO2+".RSC ADVANCES 7.20(2017):12236-12246.