Evaluation of f -element borate chemistry
Evaluation of f -element borate chemistry
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DOI：
10.1016/j.ccr.2016.02.015
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发表时间：
2016-09
影响因子：
20.6
通讯作者：
M. A. Silver;T. Albrecht‐Schmitt
中科院分区：
文献类型：
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作者：
M. A. Silver;T. Albrecht‐Schmitt
大量新的含氟硼酸盐的合成、结构解析和光谱测量揭示了这种富电子含氧阴离子对镧系元素和锕系元素电子性质的不寻常影响。这些研究的目的之一是提供模型的锕系化合物，可能存在于玻璃化的核废料或位于盐矿床内的存储库，具有显着的硼酸盐含量。此外，聚硼酸盐网络的辐射损伤弹性定位这些材料作为合适的候选人探测协调化学和物理性质更深的锕系元素系列比通常可能的，和化合物的锕系元素高达califorylate（Z= 98）已成功地制备和其特征在于精致的细节。这些材料的结构测定表明，镧系元素和锕系元素都显示出以前未知的配位化学，但更重要的是，这两个系列在结构和组成方面几乎没有重叠，并且几乎没有平行之处。此外，其中一些化合物显示出独特的物理化学性质，其中一个例子是选择性捕获放射性核素。在锕系元素硼酸盐中首次发现的最重要的发现是，加利福尼亚的化学性质代表了前所未有的化学行为的开始，与高氧化态的早期过渡金属络合物相比，它比早期元素更好。
The synthesis, structure elucidation, and spectroscopic measurements of a myriad of new,f-element borates has revealed the unusual effects that this electron-rich oxoanion has on the electronic properties of lanthanides and actinides. One purpose of these studies was to provide models for actinide compounds that may exist in either vitrified nuclear waste or in repositories located within salt deposits that have significant borate content. In addition, the radiation-damage resilience of polyborate networks positions these materials as suitable candidates for probing coordination chemistry and physical properties much deeper into the actinide series than is normally possible, and compounds with actinides up to californium (Z= 98) have been successfully prepared and characterized in exquisite detail. Structural determination of these materials show that both the lanthanide and actinide series display previously unknown coordination chemistry, but, more importantly, that the two series have little overlap in terms of structure and composition, and have few parallels. In addition, some of these compounds display unique physico-chemical properties, one example of which is the selective trapping of radionuclides. The foremost discovery first identified in actinide borates is that the chemistry of californium represents an onset of unprecedented chemical behavior that compares better with high-oxidation state, early transition metal complexes than it does with earlierf-elements.