[An(H2O)9](CF3SO3)3 (An=U–Cm, Cf): Exploring Their Stability, Structural Chemistry, and Magnetic Behavior by Experiment and Theory

Apostolidis, Christos; Schimmelpfennig, Bernd; Magnani, N.; Lindqvist‐Reis, Patric; Walter, Olaf; Sykora, Richard E.; Morgenstern, Alfred; Colineau, E.; Caciuffo, R.; Klenze, R.; Haire, R.G.; Rébizant, J.; Bruchertseifer, Frank; Fanghänel, Thomas

doi:10.1002/anie.201001077

Cited by 89 publications

(90 citation statements)

References 61 publications

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“…5). This similarity between Ln 3+ and An 3+ globally holds, confirming what was suggested by Apostolidis et al 46 and Dupouy et al, 89 for which also the light An 3+ ions behave similarly to Ln 3+ reflecting mainly the electrostatic nature of the An-O and Ln-O interaction in liquid water. By inspecting simulation details, we can notice a shift in hydration properties between Ln and corresponding An ions that is not constant across the series from one row position to the other.…”

Section: Discussionsupporting

confidence: 87%

“…[38][39][40] While this was done for many transition metals 39,[41][42][43] and lanthanoids(III), 44,45 there are no coupled systematic studies reported for the whole An 3+ series in liquid water. Recently, stability, structural parameters, and magnetic behavior were reported for most of the light actinoids(III)-from U to Cm and Cf-by experiments in crystals and theoretical calculations, 46 suggesting that the aqueous chemistry of these An 3+ ions is very similar to that of the Ln 3+ ions. Only geometry optimization in implicit solvents were reported on the whole series, 47 but from such studies it is not possible to fully understand hydration structure and dynamics in liquid phase.…”

Section: Introductionmentioning

confidence: 99%

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Polarizable interaction potential for molecular dynamics simulations of actinoids(III) in liquid water

Duvail

Martelli

Vitorge

et al. 2011

The Journal of Chemical Physics

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In this work, we have developed a polarizable classical interaction potential to study actinoids(III) in liquid water. This potential has the same analytical form as was recently used for lanthanoid(III) hydration [M. Duvail, P. Vitorge, and R. Spezia, J. Chem. Phys. 130, 104501 (2009)]. The hydration structure obtained with this potential is in good agreement with the experimentally measured ion-water distances and coordination numbers for the first half of the actinoid series. In particular, the almost linearly decreasing water-ion distance found experimentally is replicated within the calculations, in agreement with the actinoid contraction behavior. We also studied the hydration of the last part of the series, for which no structural experimental data are available, which allows us to provide some predictive insights on these ions. In particular we found that the ion-water distance decreases almost linearly across the series with a smooth decrease of coordination number from nine to eight at the end.

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Section: Discussionsupporting

confidence: 87%

Section: Introductionmentioning

confidence: 99%

Polarizable interaction potential for molecular dynamics simulations of actinoids(III) in liquid water

Duvail

Martelli

Vitorge

et al. 2011

The Journal of Chemical Physics

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“…9,31,52 We note that many of the coordination numbers determined by EXAFS for the actinide and lanthanide +3 aquo ions were larger than those observed by single crystal X-diffraction, where coordination numbers larger than 9 have yet to be reported. 13,26,30,53−62 …”

Section: Resultsmentioning

confidence: 99%

Synthesis and Characterization of the Actinium Aquo Ion

et al. 2017

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Metal aquo ions occupy central roles in all equilibria that define metal complexation in natural environments. These complexes are used to establish thermodynamic metrics (i.e., stability constants) for predicting metal binding, which are essential for defining critical parameters associated with aqueous speciation, metal chelation, in vivo transport, and so on. As such, establishing the fundamental chemistry of the actinium(III) aquo ion (Ac-aquo ion, Ac(H2O)x3+) is critical for current efforts to develop 225Ac [t1/2 = 10.0(1) d] as a targeted anticancer therapeutic agent. However, given the limited amount of actinium available for study and its high radioactivity, many aspects of actinium chemistry remain poorly defined. We overcame these challenges using the longer-lived 227Ac [t1/2 = 21.772(3) y] isotope and report the first characterization of this fundamentally important Ac-aquo coordination complex. Our X-ray absorption fine structure study revealed 10.9 ± 0.5 water molecules directly coordinated to the AcIII cation with an Ac–OH2O distance of 2.63(1) Å. This experimentally determined distance was consistent with molecular dynamics density functional theory results that showed (over the course of 8 ps) that AcIII was coordinated by 9 water molecules with Ac–OH2O distances ranging from 2.61 to 2.76 Å. The data is presented in the context of other actinide(III) and lanthanide(III) aquo ions characterized by XAFS and highlights the uniqueness of the large AcIII coordination numbers and long Ac–OH2O bond distances.

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“…As such, the variation in ionic radius is the main physical quantity that affects hydration properties. 22,23 The fact that ionic radii can dictate the complexation properties has also been pointed out for the case of ligands that are potentially less hard than water, like hexacyanoferrate. 24 Nevertheless, carbonates are softer ligands than water, and it is also possible that the metal-ligand interaction may change across the spectrum of the lanthanoid series.…”

Section: Introductionmentioning

confidence: 98%

Electronic structure and bonding of lanthanoid(iii) carbonates

Jeanvoine

Miró

Martelli

et al. 2012

Phys. Chem. Chem. Phys.

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Quantum chemical calculations were employed to elucidate the structural and bonding properties of La(III) and Lu(III) carbonates. These elements are found at the beginning and end of the lanthanoid series, respectively, and we investigate two possible metal-carbonate stoichiometries (tri- and tetracarbonates) considering all possible carbonate binding motifs, i.e., combinations of mono- and bidentate coordination. In the gas phase, the most stable tricarbonate complexes coordinate all carbonates in a bidentate fashion, while the most stable tetracarbonate complexes incorporate entirely monodentate carbonate ligands. When continuum aqueous solvation effects are included, structures having fully bidentate coordination are the most favorable in each instance. Investigation of the electronic structures of these species reveals the metal-ligand interactions to be essentially devoid of covalent character.

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[An(H₂O)₉](CF₃SO₃)₃ (An=U–Cm, Cf): Exploring Their Stability, Structural Chemistry, and Magnetic Behavior by Experiment and Theory

Cited by 89 publications

References 61 publications

Polarizable interaction potential for molecular dynamics simulations of actinoids(III) in liquid water

Polarizable interaction potential for molecular dynamics simulations of actinoids(III) in liquid water

Synthesis and Characterization of the Actinium Aquo Ion

Electronic structure and bonding of lanthanoid(iii) carbonates

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