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首页> 外文期刊>RSC Advances >Crystallization of colourless hexanitratoneptunate(iv) with anhydrous H+ countercations trapped in a hydrogen bonded polymer with diamide linkers
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Crystallization of colourless hexanitratoneptunate(iv) with anhydrous H+ countercations trapped in a hydrogen bonded polymer with diamide linkers

机译：用无水H +反应的无色六硝基替肽（IV）结晶，捕获氢键聚合物与酰胺接头

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摘要

Colourless crystalline compounds of centrosymmetric [Np(NO _(3) ) _(6) ] ~(2?) were yielded from 3 M HNO _(3) aq in the presence of double-headed 2-pyrrolidone derivatives ( L ). In the obtained crystal structures, H ~(+) was also involved as a countercation to compensate for the negative charge of [Np(NO _(3) ) _(6) ] ~(2?) , where the initial hydration around H ~(+) was fully removed during crystallization despite it having the strongest hydration enthalpy. Instead, this anhydrous H ~(+) was captured by L to form a [H ~(+) ? L ] _( n ) hydrogen bonded polymer. In [Np(NO _(3) ) _(6) ] ~(2?) , the Np ~(4+) centre is twelve-coordinated with 6 bidentate NO _(3) ~(?) , and therefore, present in an icosahedral geometry bearing inversion centre. In such a centrosymmetric system, any f–f transitions stemming from the 5f ~(3) electronic configuration of Np ~(4+) are electric-dipole forbidden. This is the reason why the compounds currently obtained were colourless unlike ordinary Np( IV ) species, which are olive-green.
机译：在双头2-吡咯烷酮衍生物（L）存在下，在3M HNO _（3）AQ中产生无色晶体化合物[NP（NO _（3））_（6）]〜（2？）。在所获得的晶体结构中，H〜（+）也涉及到补偿[NP（NO _（3））_（6）]〜（2？）的负电荷，其中初始水合物尽管它具有最强的水合焓，但在结晶期间完全除去〜（+）。相反，通过L捕获这种无水H〜（+）以形成[H〜（+）吗？ l] _（n）氢键聚合物。在[np（no _（3））_（6）]〜（2？）中，NP〜（4+）中心是12个配位，具有6个双齿NO _（3）〜（？），因此存在在ICOSAHEDRAL几何轴承倒置中心。在这样的亚离子系统中，源于5F〜（3）的NP〜（4+）的电子配置的任何F-F转换都是禁止电偶极子。这就是为什么当前获得的化合物与普通的NP（IV）物种不同，这是橄榄绿的。

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