Electronic Structure and Magnetic Properties of Dioxo-Bridged Diuranium Complexes with Diamond-Core Structural Motifs: A Relativistic DFT Study

Teyar B, Belkhiri L, Costuas K, Boucekkine A, Meyer K (2016)

Publication Type: Journal article

Publication year: 2016

Journal

Inorganic Chemistry American Chemical Society

Book Volume: 55

Pages Range: 2870-2881

Journal Issue: 6

DOI: 10.1021/acs.inorgchem.5b02704

Abstract

Electronic structures and magnetic properties of the binuclear bis(μ-oxo) U^IV/U^IV K2[{((^nP,MeArO)3tacn)U^IV}2(μ-O)2] and U^V/U^V [{((^nP,MeArO)3tacn)U^V}2(μ-O)2] (tacn = triazacyclononane, nP = neopentyl) complexes, exhibiting [U(μ-O)2U] diamond-core structural motifs, have been investigated computationally using scalar relativistic Density Functional Theory (DFT) combined with the Broken Symmetry (BS) approach for their magnetic properties. Using the B3LYP hybrid functional, the BS ground state of the pentavalent [U^V(μ-O)2U^V] 5f¹-5f¹ complex has been found of lower energy than the high spin (HS) triplet state, thus confirming the antiferromagnetic character in agreement with experimental magnetic susceptibility measurements. The nonmagnetic character observed for the tetravalent K2[U^IV(μ-O)2U^IV] 5f²-5f² species is also predicted by our DFT calculations, which led practically to the same energy for the HS and BS states. As reported for related dioxo diuranium(V) systems, superexchange is likely to be responsible for the antiferromagnetic coupling through the π-network orbital pathway within the (μ-O)2 bridge, the dissymmetrical structure of the U2O2 core playing a determining role. In the case of the U^IV species, our computations indicate that the K⁺ counterions are likely to play a role for the observed magnetic property. Finally, the MO analysis, in conjunction with NPA and QTAIM analyses, clarify the electronic structures of the studied complexes. In particular, the fact that the experimentally attempted chemical oxidation of the U^V species does not lead straightforwardly to binuclear complexes U^VI is clarified by the MO analysis.

Authors with CRIS profile

Karsten Meyer Lehrstuhl für Anorganische und Allgemeine Chemie

Involved external institutions

Université de Rennes 1 / University of Rennes 1

France (FR) Université Constantine 1

Algeria (DZ)

How to cite

APA:

Teyar, B., Belkhiri, L., Costuas, K., Boucekkine, A., & Meyer, K. (2016). Electronic Structure and Magnetic Properties of Dioxo-Bridged Diuranium Complexes with Diamond-Core Structural Motifs: A Relativistic DFT Study. Inorganic Chemistry, 55(6), 2870-2881. https://doi.org/10.1021/acs.inorgchem.5b02704

MLA:

Teyar, Billel, et al. "Electronic Structure and Magnetic Properties of Dioxo-Bridged Diuranium Complexes with Diamond-Core Structural Motifs: A Relativistic DFT Study." Inorganic Chemistry 55.6 (2016): 2870-2881.

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