Extraction and complexation of trivalent americium and lanthanides using an asymmetric picolinic acid-derived tridentate N,O-hybrid ligand†

IF 3.5 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR
Hong Cao, Yuxiao Guo, Bin Li, Qilong Tang, Huaixin Hao, Zhipeng Wang and Chao Xu
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引用次数: 0

Abstract

The extraction and complexation of trivalent americium (Am) and lanthanides (Ln) using an asymmetric picolinic acid-derived tridentate N,O-hybrid ligand, 6-(dioctylcarbamoyl)picolinic acid (DOAPA), have been studied through both experimental and theoretical methods. DOAPA exhibits effective and fast extraction of Am(III) and Ln(III). The extraction is driven by favorable enthalpy change. Slope analysis, absorption spectroscopy and NMR titration indicate that both Am(III) and Ln(III) coordinate with DOAPA to form complexes of a 1 : 3 stoichiometry (metal to ligand). Meanwhile, luminescence and mass spectral studies suggest that three deprotonated tridentate DOAPA ligands (L) substitute all the H2O molecules in the primary coordination sphere of Eu(III), resulting in the extraction of a neutral complex into the organic phase. Further theoretical calculations reveal that a more robust interaction between DOAPA and Am(III) relative to Eu(III) as well as a higher degree of covalence in Am–N/O bonds than in Eu–N/O bonds leads to slight selectivity of Am(III) over Eu(III).

Abstract Image

不对称吡啶酸衍生的三齿N, o杂化配体萃取和络合三价镅和镧系元素
通过实验和理论研究了不对称吡啶酸衍生的三齿N, o杂化配体6-(二辛基氨基甲酸酯)吡啶酸(DOAPA)对三价镅(Am)和镧系元素(Ln)的萃取和络合作用。DOAPA对Am(III)和Ln(III)具有高效、快速的萃取效果。萃取是由有利的焓变驱动的。斜率分析、吸收光谱和核磁共振滴定表明,Am(III)和Ln(III)均与DOAPA配位形成1:3化学计量的配合物(金属与配体)。同时,发光和质谱研究表明,三个去质子化的三齿DOAPA配体(L-)取代了Eu(III)初级配位球中的所有H2O分子,导致中性配合物被萃取到有机相中。进一步的理论计算表明,相对于Eu(III), DOAPA与Am(III)之间更强的相互作用以及Am- n /O键的共价程度高于Eu- n /O键,导致Am(III)对Eu(III)的选择性较低。
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来源期刊
Dalton Transactions
Dalton Transactions 化学-无机化学与核化学
CiteScore
6.60
自引率
7.50%
发文量
1832
审稿时长
1.5 months
期刊介绍: Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.
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