Structural reinvestigation of the photoluminescent complex [NdCl2(H2O)6]Cl

Hsieh, Kuan-Ying; Bendeif, El‐Eulmi; Pillet, Sébastien; Doudouh, Abdelatif; Schaniel, Dominik; Woike, Theo

doi:10.1107/s0108270113021367

Cited by 4 publications

(2 citation statements)

References 21 publications

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“…Variations in the Am–Cl bond distances were not surprising since similar trends reported were for the size matched Nd 3+ (ionic radii for six coordinate = 0.975 and 0.983 Å for Am III and Nd III , respectively). For example, the Nd–Cl mean distance in NdCl 6 3– was 0.16 to 0.08 Å shorter than in NdCl 3 and NdCl 2 (H 2 O) 6 1+ . , …”

Section: Results and Discussionmentioning

confidence: 86%

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Covalency in Americium(III) Hexachloride

et al. 2017

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Developing a better understanding of covalency (or orbital mixing) is of fundamental importance. Covalency occupies a central role in directing chemical and physical properties for almost any given compound or material. Hence, the concept of covalency has potential to generate broad and substantial scientific advances, ranging from biological applications to condensed matter physics. Given the importance of orbital mixing combined with the difficultly in measuring covalency, estimating or inferring covalency often leads to fiery debate. Consider the 60-year controversy sparked by Seaborg and co-workers ( Diamond, R. M.; Street, K., Jr.; Seaborg, G. T. J. Am. Chem. Soc. 1954 , 76 , 1461 ) when it was proposed that covalency from 5f-orbitals contributed to the unique behavior of americium in chloride matrixes. Herein, we describe the use of ligand K-edge X-ray absorption spectroscopy (XAS) and electronic structure calculations to quantify the extent of covalent bonding in-arguably-one of the most difficult systems to study, the Am-Cl interaction within AmCl. We observed both 5f- and 6d-orbital mixing with the Cl-3p orbitals; however, contributions from the 6d-orbitals were more substantial. Comparisons with the isoelectronic EuCl indicated that the amount of Cl 3p-mixing with Eu 5d-orbitals was similar to that observed with the Am 6d-orbitals. Meanwhile, the results confirmed Seaborg's 1954 hypothesis that Am 5f-orbital covalency was more substantial than 4f-orbital mixing for Eu.

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Section: Results and Discussionmentioning

confidence: 86%

“…1+ . 112,113 The UV−vis−NIR absorbance spectrum collected on single crystals of (PPh 4 ) 3 AmCl 6 was dominated by an intense absorption band at high energy (>28 570 cm −1 ), Figure 3. Superimposed on this charge transfer band were Laporte forbidden 5f → 5f transitions, characteristic of Am III .…”

Section: ■ Results and Discussionmentioning

confidence: 99%