Axially Symmetric U−O−Ln‐ and U−O−U‐Containing Molecules from the Control of Uranyl Reduction with Simple f‐Block Halides

Arnold, Polly L.; Cowie, Bradley E.; Suvova, Markéta; Zegke, Markus; Magnani, N.; Colineau, E.; Griveau, Jean‐Christophe; Caciuffo, R.; Love, Jason B.

doi:10.1002/ange.201705197

Cited by 7 publications

(2 citation statements)

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“…One of the first magnetic systems which was theoretically investigated by DFT/BS computations, is the bis(imido) pentavalent diuranium(V) [U(N t Bu) 2 (I)( t Bu 2 bpy)] 2 complex reported by Kiplinger's group in 2009 [106]. This system exhibits significant AF coupling between the two metallic 5f 1 /5f 1 spin centers, as shown by the magnetic molar χ versus T, through CCI between [U(NR) 2 ] + moieties similar to that observed in poly-uranyl [UO 2 ] + systems [23][24][25][26][27][28][29][30][31][32][46][47][48][49][50][51]59,61,69,[114][115][116]. The authors carried out B3LYP computations, employing the Stuttgart RSC 1997 ECP basis set for uranium.…”

Section: Magnetic Exchange Coupling In Actinide Bimetallic Systemsmentioning

confidence: 68%

“…As reviewed recently [71,72], a successful route to super-exchange effects in actinide-containing multinuclear species is through cation-cation interactions (CCI) [23][24][25][26][27][28][29][30][31][32][33][46][47][48][49][50][51]59,61,69,[114][115][116]123], mostly between uranyl(V) UO2 + of actinyl units. This linkage forms an oxo-bridge between metal centers affording a great number of oxo-bridged systems exhibiting significant coupling between U V centers [27,49], mixed U V /transition metal [28][29][30][31][32]111] or lanthanide centers [47,112,123], with the largest actinide-based multinuclear complex affording the unique structure of a wheel-shaped cluster {[UO2(salen)]2Mn(Py)3}6 (Py = pyridine) which is assembled through UO2 + and Mn II interactions [29]. Additionally, CCIs were observed between Np IV /Np V ions in neptunyl complexes [75].…”

Section: Magnetochemistry 2018 4 X For Peer Review 3 Of 31mentioning

confidence: 99%

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DFT Investigations of the Magnetic Properties of Actinide Complexes

2019

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Over the past 25 years, magnetic actinide complexes have been the object of considerable attention, not only at the experimental level, but also at the theoretical one. Such systems are of great interest, owing to the well-known larger spin–orbit coupling for actinide ions, and could exhibit slow relaxation of the magnetization, arising from a large anisotropy barrier, and magnetic hysteresis of purely molecular origin below a given blocking temperature. Furthermore, more diffuse 5f orbitals than lanthanide 4f ones (more covalency) could lead to stronger magnetic super-exchange. On the other hand, the extraordinary experimental challenges of actinide complexes chemistry, because of their rarity and toxicity, afford computational chemistry a particularly valuable role. However, for such a purpose, the use of a multiconfigurational post-Hartree-Fock approach is required, but such an approach is computationally demanding for polymetallic systems—notably for actinide ones—and usually simplified models are considered instead of the actual systems. Thus, Density Functional Theory (DFT) appears as an alternative tool to compute magnetic exchange coupling and to explore the electronic structure and magnetic properties of actinide-containing molecules, especially when the considered systems are very large. In this paper, relevant achievements regarding DFT investigations of the magnetic properties of actinide complexes are surveyed, with particular emphasis on some representative examples that illustrate the subject, including actinides in Single Molecular Magnets (SMMs) and systems featuring metal-metal super-exchange coupling interactions. Examples are drawn from studies that are either entirely computational or are combined experimental/computational investigations in which the latter play a significant role.

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Section: Magnetic Exchange Coupling In Actinide Bimetallic Systemsmentioning

confidence: 68%

Section: Magnetochemistry 2018 4 X For Peer Review 3 Of 31mentioning

confidence: 99%

DFT Investigations of the Magnetic Properties of Actinide Complexes

2019

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Neue Mitglieder der Royal Society: P. L. Arnold, M. A. Brimble, F. Caruso, R. S. Goody, R. H. Crabtree, C. Bertozzi, J. Sauer / Jochen‐Block‐Preis: A. Vorholt / Otto‐Bayer‐Preis: T. Erb

2018

Angewandte Chemie

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Ligand‐Supported Facile Conversion of Uranyl(VI) into Uranium(IV) in Organic and Aqueous Media

et al. 2020

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Reduction of uranyl(VI) to U V and to U IV is important in uranium environmental migration and remediation processes. The anaerobic reduction of a uranyl U VI complex supported by a picolinate ligand in both organic and aqueous media is presented. The [U VI O 2 (dpaea)] complex is readily converted into the cis-boroxide U IV species via diborane-mediated reductive functionalization in organic media. Remarkably, in aqueous media the uranyl(VI) complex is rapidly converted, by Na 2 S 2 O 4 , a reductant relevant for chemical remediation processes, into the stable uranyl(V) analogue, which is then slowly reduced to yield a waterinsoluble trinuclear U IV oxo-hydroxo cluster. This report provides the first example of direct conversion of a uranyl(VI) compound into a well-defined molecular U IV species in aqueous conditions. 1015 Lausanne (Switzerland)

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Axially Symmetric U−O−Ln‐ and U−O−U‐Containing Molecules from the Control of Uranyl Reduction with Simple f‐Block Halides

Cited by 7 publications

References 44 publications

DFT Investigations of the Magnetic Properties of Actinide Complexes

DFT Investigations of the Magnetic Properties of Actinide Complexes

Neue Mitglieder der Royal Society: P. L. Arnold, M. A. Brimble, F. Caruso, R. S. Goody, R. H. Crabtree, C. Bertozzi, J. Sauer / Jochen‐Block‐Preis: A. Vorholt / Otto‐Bayer‐Preis: T. Erb

Ligand‐Supported Facile Conversion of Uranyl(VI) into Uranium(IV) in Organic and Aqueous Media

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