C-N偶联邻菲罗啉衍生双（吡唑）配体选择性分离Am(III)/Eu（III）

IF 4.7 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Pub Date : 2025-10-14 DOI:10.1021/acs.inorgchem.5c03092

Tengfei Cui,Qing Chang,Qiao Chen,Zhen Xu,Qiang Jin,Zongyuan Chen,Yin Wang,Zhipeng Wang,Zhijun Guo

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引用次数: 0

摘要

从镧系元素（Ln(III)）中分离三价锕系元素（An(III)）是核废料管理中的一项重大挑战，因为它能够降低长期放射性毒性并支持先进的燃料循环战略。在此，我们报道了一系列由2,9-二氯-1,10-菲罗啉（Phen）和吡唑（Pz）衍生物直接C-N偶联反应得到的四齿n -供体配体（L1-L4），即2,9-二（1h -吡罗啉-1-基）-1,10-菲罗啉（L1）， 2,9-二（4-乙基- 1h -吡罗啉-1-基）-1,10-菲罗啉（L2）， 2,9-二（4-丁基- 1h -吡罗啉-1-基）-1,10-菲罗啉（L3）和2,9-二（3-丁基- 1h -吡罗啉-1-基）-1,10-菲罗啉（L4）。这些配体表现出优异的Am（III）萃取效率和选择性，在高酸性HNO3介质中实现了超过220的分离因子（sfm /Eu）。坡面分析和电喷雾质谱（ESI-MS）证实了提取物种的1:1 M/L化学计量。系统紫外-可见滴定和单晶x射线衍射研究表明，溶液和固体中存在类似的1:1配位结构。Eu（III）的稳定性常数为L3(5.92±0.08)> L2(5.75±0.11)> L1(5.56±0.06)> L4(5.31±0.02)，反映了烷基取代基对配体吡唑基团的诱导效应和位阻的相互作用。这项工作强调了c - n偶联双（吡唑）菲罗啉配体作为酸性条件下An(III)/Ln（III）分离的高选择性萃取剂的潜力。

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Selective Am(III)/Eu(III) Separation by C-N Coupling Phenanthroline-Derived Bis(pyrazole) Ligands.

The separation of trivalent actinides (An(III)) from lanthanides (Ln(III)) is a critical challenge in nuclear waste management, as it enables the reduction of long-term radiotoxicity and supports advanced fuel cycle strategies. Herein, we report a series of tetradentate N-donor ligands (L1-L4) derived from a straightforward C-N coupling reaction between 2,9-dichloro-1,10-phenanthroline (Phen) and pyrazole (Pz) derivatives, i.e., 2,9-bis(1H-pyrazol-1-yl)-1,10-phenanthroline (L1), 2,9-bis(4-ethyl-1H-pyrazol-1-yl)-1,10-phenanthroline (L2), 2,9-bis(4-butyl-1H-pyrazol-1-yl)-1,10-phenanthroline (L3), and 2,9-bis(3-butyl-1H-pyrazol-1-yl)-1,10-phenanthroline (L4). These ligands exhibit exceptional Am(III) extraction efficiency and selectivity, achieving separation factors (SFAm/Eu) exceeding 220 in highly acidic HNO3 media. Slope analysis and electrospray ionization mass spectrometry (ESI-MS) confirmed a 1:1 M/L stoichiometry for the extracted species. Systematic UV-vis titration and single-crystal X-ray diffraction studies revealed an analogous 1:1 coordination structure in solution and solid states. The stability constants for Eu(III) followed the trend of L3 (5.92 ± 0.08) > L2 (5.75 ± 0.11) > L1 (5.56 ± 0.06) > L4 (5.31 ± 0.02), reflecting the interplay of inductive effects and steric hindrance imposed by alkyl substituents on the pyrazole moieties of the ligands. This work highlights the potential of C-N-coupled bis(pyrazole)phenanthroline ligands as highly selective extractants for An(III)/Ln(III) separation under acidic conditions.

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来源期刊

Inorganic Chemistry 化学-无机化学与核化学

CiteScore

7.60

自引率

13.00%

发文量

1960

审稿时长

1.9 months

期刊介绍： Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.