A Walk Across the Lanthanide Series: Trend in Affinity for Phosphate and Stability of Lanthanide Receptors from La(III) to Lu(III).
A Walk Across the Lanthanide Series: Trend in Affinity for Phosphate and Stability of Lanthanide Receptors from La(III) to Lu(III).
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DOI：
10.1021/acs.inorgchem.1c02462
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发表时间：
2021-10-18
影响因子：
4.6
通讯作者：
Pierre VC
中科院分区：
文献类型：
--
作者：
Wilharm RK;Huang SY;Gugger IJ;Pierre VC
通过与中心铕（III）类似物的竞争，利用发光光谱研究了两种1,2-羟基吡啶酸镧系（III）受体LnIII-2,2- li - hopo和LnIII-3,3- gly - hopo （LnIII = LaIII, PrIII, NdIII, SmIII, EuIII, GdIII, TbIII, DyIII, HoIII, ErIII, TmIII， YbIII和LuIII）对磷酸盐的亲和力趋势。不管配体是什么，稀土受体对其磷酸盐客体的亲和力在整个系列中都表现出急剧而持续的增加，其中较晚的镧系元素对氧阴离子的亲和力最高。这一趋势反映了镧系受体的稳定性，从LaIII到LuIII，镧系受体的稳定性也显著且持续地增加。对于这两种配体，稀土的离子半径（一个与它的刘易斯酸度直接相关的参数）与它对阴离子的亲和力密切相关，而不管这个阴离子是配位离子（在这种情况下是1,2-羟基吡啶酸配体）还是镧系元素受体靶向的客体（在这种情况下是磷酸盐）。这些观察结果表明磷酸盐配位缺乏位阻。有利的是，镧系元素受体的有效性增加了，稳定性也增加了。luiii -2,2- li - hopo的高稳定性，加上对磷酸盐的高亲和力，使其成为一个特别有前途的转化应用于磷酸盐的医疗或环境封存，因为更高的稳定性将进一步降低阴离子分离过程中稀土浸出的风险。两种镧系配合物在稳定性上的巨大差异——2,2- li - hopo的LuIII配合物比LaIII配合物稳定至少7个数量级——预示着在稀土分离方面的潜在应用。随着离子半径的减小和金属的Lewis酸度的增加，镧系镧（III）配合物对磷酸盐的亲和力和稳定性在镧系镧系中从镧（III）到镥（III）稳定而急剧地增加。这些趋势表明，空间位阻对配体或磷酸盐配位都不是一个重要的影响因素。
The trend in affinity of two 1,2-hydroxypyridinonate lanthanide(III) receptors—LnIII-2,2-Li-HOPO and LnIII-3,3-Gly-HOPO (LnIII = LaIII, PrIII, NdIII, SmIII, EuIII, GdIII, TbIII, DyIII, HoIII, ErIII, TmIII, YbIII, and LuIII)—for phosphate across the series was investigated by luminescence spectroscopy via competition against the central europium(III) analog. Regardless of the ligand, the rare earth receptors display a steep and continuous increase in affinity for their phosphate guest across the series, with the later lanthanides displaying the highest affinity for the oxyanion. This trend mirrors that of the stability of the lanthanide receptors, which also increases significantly and continuously from LaIII to LuIII. For these two ligands, the ionic radius of a rare earth, a parameter directly linked to its Lewis acidity, correlates strongly with its affinity for anions, regardless of whether that anion is the one coordinating it (in this case the 1,2-hydroxypyridinonate ligand) or the guest targeted by the lanthanide receptor (in this case phosphate). These observations are indicative of a lack of steric hindrance for coordination of phosphate. Advantageously, increased efficacy of the lanthanide receptor comes with increased stability. The remarkably high stability of LuIII-2,2-Li-HOPO, combined with its high affinity for phosphate, makes it a particularly promising candidate for translational application to medical or environmental sequestration of phosphate since the higher stability will further reduce the risk of the rare earth leaching during anion separation. The unusually large difference in stability between lanthanide complexes—the LuIII complex of 2,2-Li-HOPO is at least seven orders of magnitude more stable than the LaIII one—bodes well for potential applications in rare earth separation. The affinity for phosphate and the stability of tripodal lanthanide(III) complexes increase steadily and steeply from lanthanum(III) to lutetium(III) across the lanthanide series as the ionic radii decreases and Lewis acidity of the metal increases. These trends indicate that steric hindrance is not a significant contributing factor to either ligand or phosphate coordination.
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影响因子：
20.6
作者：
Alderighi, L;Gans, P;Vacca, A
通讯作者：
Vacca, A
影响因子：
4.6
作者：
Doble, DMJ;Melchior, M;Raymond, KN
通讯作者：
Raymond, KN
DOI：
10.1016/0022-1902(62)80236-x
发表时间：
1962-01-01
期刊：
JOURNAL OF INORGANIC & NUCLEAR CHEMISTRY
影响因子：
--
作者：
MOELLER, T;THOMPSON, LC
通讯作者：
THOMPSON, LC
影响因子：
7
作者：
Baranyas, Zsolt;Castetli, Daniela Delti;Botta, Mauro
通讯作者：
Botta, Mauro
影响因子：
18.3
作者：
Cable, Morgan L.;Kirby, James P.;Gray, Harry B.;Ponce, Adrian
通讯作者：
Ponce, Adrian