Tetrameric entity resulting from two distinct dinuclear uranyl-centered motifs bridged through μ2-OH and pyridazine-3,6-dicarboxylate

Henry, Natacha; Lagrenée, Michel; Loiseau, Thierry; Clavier, Nicolas; Dacheux, Nicolas; Abraham, Francis

doi:10.1016/j.inoche.2010.12.019

Cited by 24 publications

(9 citation statements)

References 44 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In this structure, the uranyl groups of [(UO 2 ) 2 (H 2 O) 6 (OH) 2 ] 2+ are bridged by hydroxo ligands and their equatorial coordination spheres are satisfied by aquo ligands. Similar μ-hydroxo bridged structures have also been obtained for other actinide complexes. − On the basis of these prior works in the solid and aqueous phases, , it could be assumed that the structures of the gaseous [(UO 2 ) 2 (OH) n ] 4– n species would conform to the μ 2 -dihydroxo structural format. It is therefore intriguing to examine the relative stabilities of this format with respect to structures featuring CCIs between the two uranyl groups.…”

Section: Introductionmentioning

confidence: 60%

Cation–Cation Interactions in [(UO₂)₂(OH)_n]^4–n Complexes

et al. 2013

View full text Add to dashboard Cite

The structures and bonding of gas-phase [(UO2)2(OH)n](4-n) (n = 2-6) complexes have been studied using density functional theory (DFT), MP2, and CCSD(T) methods with particular emphasis on ground state structures featuring cation-cation interactions (CCIs) between the uranyl groups. An interesting trend is observed in the stabilities of members of this series of complexes. The structures of [(UO2)2(OH)2](2+), [(UO2)2(OH)4], and [(UO2)2(OH)6](2-) featuring CCIs are found at higher energies (by 3-27 kcal/mol) in comparison to their conventional μ2-dihydroxo structures. In contrast, the CCI structures of [(UO2)2(OH)3](+) and [(UO2)2(OH)5](-) are respectively degenerate with and lower in energy than the structures with the μ2-dihydroxo format. The origin of this trend lies in the symmetry-based need to balance the coordination numbers and effective atomic charges of each uranium center. The calculated IR vibrational frequencies provide signature probes that can be used in differentiating the low-energy structures and in experimentally confirming the existence of the structures featuring CCIs.

show abstract

Section: Introductionmentioning

confidence: 60%

Cation–Cation Interactions in [(UO₂)₂(OH)_n]^4–n Complexes

et al. 2013

View full text Add to dashboard Cite

show abstract

“…Figure S1, Supporting Information). Lanthanides are typically 8-, 9-, or 10-coordinate when bound by oxygen atoms, yielding different coordination geometries based on square antiprisms, dodecahedra, tricapped trigonal prisms, capped triangular cupola, etc . Shape8 calculations demonstrate that the geometry for the HoO 8 unit is best described as a distorted trigonal dodecahedron with approximate D 2 d symmetry (cf.…”

Section: Resultsmentioning

confidence: 99%

Thermochromism, the Alexandrite Effect, and Dynamic Jahn–Teller Distortions in Ho₂Cu(TeO₃)₂(SO₄)₂

et al. 2013

View full text Add to dashboard Cite

A 3d-4f heterobimetallic material with mixed anions, Ho2Cu(TeO3)2(SO4)2, has been prepared under hydrothermal conditions. Ho2Cu(TeO3)2(SO4)2 exhibits both thermochromism and the Alexandrite effect. Variable temperature single crystal X-ray diffraction and UV-vis-NIR spectroscopy reveal that changes in the Cu(II) coordination geometry result in negative thermal expansion of axial Cu-O bonds that plays a role in the thermochromic transition of Ho2Cu(TeO3)2(SO4)2. Magnetic studies reveal an effective magnetic moment of 14.97 μB. which has a good agreement with the calculated value of 15.09 μB.

show abstract

“…Lanthanide and actinide cations, such as cerium and plutonium, with same oxidation state and coordination number can possess nearly identical ionic radii . In oxo-anion compounds both lanthanide and actinide can be bonded to 7, 8, 9, or 10 oxygen atoms, yielding different coordination geometries based on square antiprism, pentagonal bipyramid, hexagonal bipyramid, tricapped trigonal prism, trigonal dodecahedra, distorted dodecahedra, capped triangular cupola, etc . Lanthanides are used to simulate transuranium elements with low oxidation state to predict their behavior under long-term storage in repositories and transportation in the environment from contaminated sites .…”

Section: Introductionmentioning

confidence: 99%

Comparisons of Plutonium, Thorium, and Cerium Tellurite Sulfates

et al. 2013

View full text Add to dashboard Cite

The hydrothermal reaction of PuCl3 or CeCl3 with TeO2 in the presence of sulfuric acid under the comparable conditions results in the crystallization of Pu(TeO3)(SO4) or Ce2(Te2O5)(SO4)2, respectively. Pu(TeO3)(SO4) and its isotypic compound Th(TeO3)(SO4) are characterized by a neutral layer structure with no interlamellar charge-balancing ions. However, Ce2(Te2O5)(SO4)2 possesses a completely different dense three-dimensional framework. Bond valence calculation and UV-vis-NIR spectra indicate that the Ce compound is trivalent whereas the Pu and Th compounds are tetravalent leading to the formation of significantly different compounds. Pu(TeO3)(SO4), Th(TeO3)(SO4), and Ce2(Te2O5)(SO4)2 represent the first plutonium/thorium/cerium tellurite sulfate compounds. Our study strongly suggests that the chemistries of Pu and Ce are not the same, and this is another example of the failure of Ce as a surrogate.

show abstract

Tetrameric entity resulting from two distinct dinuclear uranyl-centered motifs bridged through μ2-OH and pyridazine-3,6-dicarboxylate

Cited by 24 publications

References 44 publications

Cation–Cation Interactions in [(UO₂)₂(OH)_n]^4–n Complexes

Cation–Cation Interactions in [(UO₂)₂(OH)_n]^4–n Complexes

Thermochromism, the Alexandrite Effect, and Dynamic Jahn–Teller Distortions in Ho₂Cu(TeO₃)₂(SO₄)₂

Comparisons of Plutonium, Thorium, and Cerium Tellurite Sulfates

Contact Info

Product

Resources

About

Tetrameric entity resulting from two distinct dinuclear uranyl-centered motifs bridged through μ2-OH and pyridazine-3,6-dicarboxylate

Cited by 24 publications

References 44 publications

Cation–Cation Interactions in [(UO2)2(OH)n]4–n Complexes

Cation–Cation Interactions in [(UO2)2(OH)n]4–n Complexes

Thermochromism, the Alexandrite Effect, and Dynamic Jahn–Teller Distortions in Ho2Cu(TeO3)2(SO4)2

Comparisons of Plutonium, Thorium, and Cerium Tellurite Sulfates

Contact Info

Product

Resources

About

Cation–Cation Interactions in [(UO₂)₂(OH)_n]^4–n Complexes

Cation–Cation Interactions in [(UO₂)₂(OH)_n]^4–n Complexes

Thermochromism, the Alexandrite Effect, and Dynamic Jahn–Teller Distortions in Ho₂Cu(TeO₃)₂(SO₄)₂