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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Impacts of hydrogen bonding interactions with Np(V/VI)O2Cl4 complexes: vibrational spectroscopy, redox behavior, and computational analysis
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Impacts of hydrogen bonding interactions with Np(V/VI)O2Cl4 complexes: vibrational spectroscopy, redox behavior, and computational analysis

机译：氢键与NP（v / vi）O 2 Cl 4复合物的影响：振动光谱，氧化还原行为和计算分析

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摘要

The neptunyl (Np(v)O-2(+)/Np(vi)O-2(2+)) cation is the dominant form of Np-237 in acidic aqueous solutions and the stability of the Np(v) and Np(vi) species is driven by the specific chemical constituents present in the system. Hydrogen bonding with the oxo group may impact the stability of these species, but there is limited understanding of how these intermolecular interactions influence the behavior of both solution and solid-state species. In the current study, we systematically evaluate the interactions between the neptunyl tetrachloride species and hydrogen donors in coordination complexes and in the related aqueous solutions. Both Np(v) compounds (N2C4H12)(2)[Np(v)O2Cl4]Cl (Np(V)pipz) and (NOC4H10)(3)[Np(v)O2Cl4] (Np(V)morph) exhibit directional hydrogen bonding to the neptunyl oxo group while Np(vi) compounds (NC5H6)(2)[Np(vi)O2Cl4] (Np(VI)pyr) and (NOC4H10)(4)[Np(vi)O2Cl4]2Cl (Np(VI)morph) assemble via halogen interactions. The Raman spectra of the solid-state phases indicate the activation of vibrational bands when there is asymmetry of the neptunyl bond, while these spectral features are not observed within the related solution phase spectra. Density functional theory calculations of the Np(V)pipz system suggest that activation of the nu(3) asymmetric stretch and other combination modes lead to additional complexity within the solid-state spectra. Electrochemical analyses of complexes in the solution phases are consistent with the results of the crystallization experiments as the voltammetric potentials of Np(v)/Np(vi) complexes in the presence of protonated heterocycles differ from the potentials of pure Np(v) and may correlate with the hydrogen bonding interactions.
机译：Neptonyl（NP（V）O-2（+）/ NP（VI）O-2（2+））阳离子是酸性水溶液中NP-237的主要形式，以及NP（V）和NP的稳定性（VI）物种由系统中存在的特定化学成分驱动。与氧代组的氢键可能影响这些物种的稳定性，但是有限地了解这些分子间相互作用如何影响溶液和固态物种的行为。在目前的研究中，我们系统地评估了四氯化物物种和氢供体之间的相互作用在配位复合物中和相关的水溶液中。 NP（V）化合物（N2C4H12）（2）[NP（V）O 2 Cl 4] Cl（NP（V）PIPZ）和（NOC 4H10）（3）[NP（V）O 2 Cl 4]（NP（V）变形）表现出向定向与Neptunyl氧代组的氢键合，而NP（VI）化合物（NC5H6）（2）[NP（VI）O 2 Cl 4]（NP（VI）Pyr）和（NOC 4H10）（4）[NP（VI）O 2 Cl 4] 2Cl（NP （vi）变形）通过卤素互动组装。当存在Neptunyl键的不对称时，固态阶段的拉曼光谱表明振动带的激活，而在相关溶液相谱内未观察到这些光谱特征。 Np个（V）pipz系统的密度泛函理论计算表明的NU（3）非对称的拉伸和其它组合方式导致额外的固态光谱内的复杂的活化。溶液相中复合物的电化学分析与作为在质子化杂环存在下的NP（V）/ NP（VI）配合物的伏安型电位的结晶实验结果与纯NP（v）的潜力不同，并且可以与氢键相互作用相关。

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