Sperling Joseph M, Gaiser Alyssa N, Windorff Cory J, Klamm Bonnie E, Whitefoot Megan A, Chemey Alexander T, Long Brian N, Campbell Joanna G, Albrecht-Schmitt Thomas E
Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, United States.
Inorg Chem. 2020 Mar 2;59(5):3085-3090. doi: 10.1021/acs.inorgchem.9b03432. Epub 2020 Feb 10.
The aqueous reaction of mellitic acid (Hmell) with PuBr·HO forms two plutonium mellitates, Pu(mell)(HO)·HO () and Pu(mell)(HO)·2HO (). These compounds are compared to the isomorphous lanthanide mellitates with similar ionic radii via bond length analysis. Both plutonium compounds form three-dimensional metal-organic frameworks, with having two unique metal centers and having one. All plutonium metal centers exhibit nine-coordinate geometries. Our results show metal-oxygen bond lengths for plutonium significantly shorter than those of the previously reported lanthanum and herein reported cerium analogues, consistent with the nine-coordinate ionic radii. Clear Laporte-forbidden 5f → 5f transitions are observed in the ultraviolet-visible-near-infrared spectra and are assigned to trivalent plutonium. However, there is a distinct color difference between the two plutonium compounds.
苯六甲酸（Hmell）与PuBr·HO的水相反应生成两种钚苯六甲酸盐，即Pu(mell)(HO)·HO（）和Pu(mell)(HO)·2HO（）。通过键长分析，将这些化合物与具有相似离子半径的同构镧系苯六甲酸盐进行比较。两种钚化合物均形成三维金属有机骨架，其中一个具有两个独特的金属中心，另一个具有一个。所有钚金属中心均呈现九配位几何结构。我们的结果表明，钚的金属-氧键长明显短于先前报道的镧以及本文报道的铈类似物，这与九配位离子半径一致。在紫外-可见-近红外光谱中观察到清晰的拉波特禁戒5f→5f跃迁，并将其归因于三价钚。然而，两种钚化合物之间存在明显的颜色差异。
