Emergence of californium as the second transitional element in the actinide series.
Emergence of californium as the second transitional element in the actinide series.
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DOI：
10.1038/ncomms7827
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发表时间：
2015-04-16
影响因子：
16.6
通讯作者：
Albrecht-Schmitt, Thomas E.
中科院分区：
文献类型：
--
作者：
Cary, Samantha K.;Vasiliu, Monica;Baumbach, Ryan E.;Stritzinger, Jared T.;Green, Thomas D.;Diefenbach, Kariem;Cross, Justin N.;Knappenberger, Kenneth L.;Liu, Guokui;Silver, Mark A.;DePrince, A. Eugene;Polinski, Matthew J.;Van Cleve, Shelley M.;House, Jane H.;Kikugawa, Naoki;Gallagher, Andrew;Arico, Alexandra A.;Dixon, David A.;Albrecht-Schmitt, Thomas E.
由于5f电子的局域化，在钚和镅之间的锕系元素中出现了周期性的中断。后来的锕系元素的化学反应被认为与镧系元素非常相似，因为它们的化学键被认为是离子键，而络合作用不应该实质性地改变金属离子的电子结构。在这里，我们证明了通过吡啶衍生物连接的加利福尼亚（III）会导致所得到的配合物的性质与预测的自由离子的性质有显著的偏差。我们通过描述镅和curium的类似物进行比较来扩展这一点，并表明这些明显的效应是由于锕系元素的周期性的第二次转变，部分原因是二价氧化态的稳定。加州（II）的亚稳态是负责许多不寻常的性质，包括加州的绿色光致发光。钚后锕系元素的化学性质被认为类似于镧系元素，因为它们的化学键主要是离子键。在这里，作者表明，由于锕系元素周期的第二次中断，加利福尼亚（III）配合物显示出与自由离子预测的明显不同的性质。
A break in periodicity occurs in the actinide series between plutonium and americium as the result of the localization of 5f electrons. The subsequent chemistry of later actinides is thought to closely parallel lanthanides in that bonding is expected to be ionic and complexation should not substantially alter the electronic structure of the metal ions. Here we demonstrate that ligation of californium(III) by a pyridine derivative results in significant deviations in the properties of the resultant complex with respect to that predicted for the free ion. We expand on this by characterizing the americium and curium analogues for comparison, and show that these pronounced effects result from a second transition in periodicity in the actinide series that occurs, in part, because of the stabilization of the divalent oxidation state. The metastability of californium(II) is responsible for many of the unusual properties of californium including the green photoluminescence. The chemistry of the post-plutonium actinides is thought to resemble lanthanides in that bonding is primarily ionic. Here, the authors show that a californium(III) complex displays significantly different properties to those predicted for the free ion owing to a second break in actinide periodicity.
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DOI：
10.1016/0020-1650(76)80122-5
发表时间：
1976-01-01
期刊：
INORGANIC & NUCLEAR CHEMISTRY LETTERS
影响因子：
--
作者：
HAIRE, RG;ASPREY, LB
通讯作者：
ASPREY, LB
影响因子：
4.6
作者：
Bray, Travis H.;Nelson, Anna-Gay D.;Albrecht-Schmitt, Thomas E.
通讯作者：
Albrecht-Schmitt, Thomas E.
影响因子：
3.7
作者：
HUBERT, S;THOUVENOT, P;EDELSTEIN, N
通讯作者：
EDELSTEIN, N
影响因子：
16.6
作者：
Lindqvist-Reis, Patric;Apostolidis, Christos;Haire, Richard G.
通讯作者：
Haire, Richard G.
影响因子：
16.6
作者：
Galbis, Elsa;Hernandez-Cobos, Jorge;Marcos, Enrique Sanchez
通讯作者：
Marcos, Enrique Sanchez