化学
取代基
芳基
X射线吸收光谱法
密度泛函理论
结晶学
戒指(化学)
镍
吸收光谱法
硫黄
分子轨道
电子结构
烷基
计算化学
立体化学
分子
有机化学
物理
量子力学
作者
Ning Pu,Chao Xu,Jing Chen
出处
期刊:Inorganic Chemistry
[American Chemical Society]
日期:2023-09-13
卷期号:62 (38): 15565-15574
被引量:1
标识
DOI:10.1021/acs.inorgchem.3c02062
摘要
Complexes of Ni(II) with a series of aryl or alkyl substituent dithiophosphinic acids were characterized by crystallographic structure, sulfur K-edge X-ray absorption spectroscopy (XAS), and density functional theory (DFT). In these complexes, Ni(II) coordinates with four sulfur atoms from two dithiophosphinate anions form a well-defined square-planar structure. Despite the minor differences in the geometry parameters among the complexes, the electronic structure is affected significantly by the substituent group attached to dithiophosphinic acid. In particular, the addition of ortho-CF3 group to the aryl ring constrains the orientation of the aryl ring and enhances the conjugation between the aryl ring and the coordinating core. Sulfur K-edge XAS spectra help further reveal the electronic structure of the complexes. Both the pre-edge feature and rising-edge feature provide abundant information on the molecular orbitals and show a distinctive effect of the substituent groups on the electronic structure of the complexes, which is supposedly relevant to the ligand’s performance in Ln(III)/An(III) separation.
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