Characterization of the binding of six actinyls AnO(2)(2+/+) (An = U/Np/Pu) with three expanded porphyrins by density functional theory

doi:10.1039/c6nj01615d

	Characterization of the binding of six actinyls AnO(2)(2+/+) (An = U/Np/Pu) with three expanded porphyrins by density functional theory
	Ding, WJ; Wang DQ(王东琪); Wang, DQ; Yang, MX
刊名	NEW JOURNAL OF CHEMISTRY
	2017
卷号	41 期号:1 页码:63-74
ISSN号	1144-0546
DOI	10.1039/c6nj01615d
文献子类	Article
英文摘要	We reported a density functional theory study on the complexation of six hydrated actinyl cations, AnO(2)(H2O)(5)(2+/+) (aq) (An = U/Np/Pu), with three expanded porphyrins, amethyrin (H(4)L1), oxasapphyrin (H(2)L2), and grandephyrin (H(3)L3). The geometries have been fully optimized and analyzed, and the electronic structures, the binding free energies, and the NMR properties were calculated. Natural population analysis and Quantum Theory of Atoms in Molecules (QTAIM) topology analysis techniques were applied to understand the interaction modes between two entities of each complex. The calculations show that for the same ligand, PuO22+ and NpO22+ display stronger binding affinity than UO22+, UO2+, NpO2+, and PuO2+, and among the three ligands tested, L2(2-) fits better with the actinyl cations than L-3(3-) and H(2)L1(2-). The redox process was observed in the complexation of PuO22+ and NpO22+ with specific ligands, which agrees with the experimental results. In the characterization of the nature of the coordination bonding interactions, QTAIM gives a consistent description with the natural population analysis method and shows that the interaction between An and the electron donor atoms in the first coordination shell has a strong ionic feature, while the interaction between An and O-yl atoms of the actinyls in the complexes remains covalent. This work complements the earlier experimental studies by providing a molecular level of understanding on the interaction between actinyls and expanded porphyrins, and is expected to contribute to the communities of the chemistry of actinides and expanded porphyrins.
电子版国际标准刊号	1369-9261
WOS关键词	MOLECULAR-ORBITAL METHODS ; INDEPENDENT CHEMICAL-SHIFTS ; EFFECTIVE CORE POTENTIALS ; GAUSSIAN-BASIS SETS ; RESPONSE PROPERTIES ; AB-INITIO ; INCLUSION COMPLEXES ; ACTINIDE CHEMISTRY ; URANIUM COMPLEXES ; AROMATICITY INDEX
WOS研究方向	Chemistry
语种	英语
WOS记录号	WOS:000391451500006
内容类型	期刊论文
源URL	[http://ir.ihep.ac.cn/handle/311005/285121]
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	Ding, WJ,Wang DQ,Wang, DQ,et al. Characterization of the binding of six actinyls AnO(2)(2+/+) (An = U/Np/Pu) with three expanded porphyrins by density functional theory[J]. NEW JOURNAL OF CHEMISTRY,2017,41(1):63-74.
APA	Ding, WJ,王东琪,Wang, DQ,&Yang, MX.(2017).Characterization of the binding of six actinyls AnO(2)(2+/+) (An = U/Np/Pu) with three expanded porphyrins by density functional theory.NEW JOURNAL OF CHEMISTRY,41(1),63-74.
MLA	Ding, WJ,et al."Characterization of the binding of six actinyls AnO(2)(2+/+) (An = U/Np/Pu) with three expanded porphyrins by density functional theory".NEW JOURNAL OF CHEMISTRY 41.1(2017):63-74.