An investigation by DFT of the electronic structure and magnetic properties of a novel μ-oxo-iron(III) complex with the 1,10-phenathroline ligand

Selmi, Wafa; Abdelhak, Jawher; Marchivie, Mathieu; Chastanet, Guillaume; Zid, Mohamed Faouzi

doi:10.1016/j.poly.2016.12.012

Cited by 8 publications

(4 citation statements)

References 66 publications

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“…The DFT/BS approach based on the hybrid functional B3LYP turns out to be reliable for a satisfying estimation of the coupling constants, not only for binuclear transition metal complexes, − but also for actinide-containing molecules, ,,,− ,,, even though the use of the DFT single-determinant approach is a subject of debate. ,− Note that alternatively, the PBE0 functional has also been used to compute the coupling between an actinide (Pu VI ) and a radical (it is known that hybrid functionals usually lead to better values of coupling constants).…”

Section: Methodsmentioning

confidence: 99%

Electronic Structure and Magneto-Structural Correlations Study of Cu₂UL Trinuclear Schiff Base Complexes: A 3d–5f–3d Case

et al. 2023

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The magnetic properties of trinuclear Schiff base complexes M 2 AnL i (M II = Zn, Cu; An IV = Th, U; L i = Schiff base; i = 1−4, 6, 7, 9), exhibiting the [M(μ-O) 2 ] 2 U core structure with adjacent M1•••U and M2•••U and nextadjacent M1•••M2 interactions, featuring 3d-5f-3d subsystems, have been investigated theoretically using relativistic ZORA/B3LYP computations combined with the broken symmetry (BS) approach. Bond order and natural population analyses reveal that the covalent contribution to the bonding within the Cu−O−U coordination is important thus favoring superexchange coupling between the transition metal and the uranium magnetic centers. The calculated coupling constants J CuU between the Cu and U atoms, agree with the observed shift from the antiferromagnetic (AF) character of the L 1,2,3,4 complexes to the ferromagnetic (ferro) of the L 6,7,9 ones. The structural parameters, i.e., the Cu•••U distances and the Cu−O−U angles, as well as the electronic factors driving the magnetic couplings are discussed. The analyses are supported by the study of the mixed ZnCuUL i and Cu 2 ThL i systems, where in the first complex the Cu II (3d 9 ) ion is replaced by the diamagnetic Zn II (3d 10 ) one, whereas in the second complex the U IV (5f 2 ) paramagnetic center is replaced by the diamagnetic Th IV (5f 0 ) one.

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Section: Methodsmentioning

confidence: 99%

Electronic Structure and Magneto-Structural Correlations Study of Cu₂UL Trinuclear Schiff Base Complexes: A 3d–5f–3d Case

et al. 2023

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“…Regarding magnetic exchange, the used spin Hamiltonian is the Heisenberg-Dirac-van Vleck (HDvV) one,Ĥ = −ΣJ ijŜi •Ŝ j whereŜ i ,Ŝ j are the spin operators associated to the magnetic centers i, j and J ij the coupling constants between these centers [82,83,90,91].…”

Section: Theoretical Approaches For Computing Exchange Coupling Constmentioning

confidence: 99%

“…Indeed, DFT emerged in the early 2000s as a powerful technique, particularly when used in combination with the hybrid B3LYP functional [86,87] and the Broken-Symmetry (BS) Noodleman's approach [88,89], for satisfactory simulations of magnetic properties. This is true not only in the case of d-transition metal systems [82,83,[90][91][92][93][94][95][96][97][98][99][100][101][102][103][104], but also for actinide-containing molecules [105][106][107]. It is worth noting that actinide-based SMMs are multiconfigurational systems, and the use of the monodeterminantal approach with DFT is a subject of debate [63,[108][109][110].…”

Section: Introductionmentioning

confidence: 99%

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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“…≈175 cm -1 ). 52 Anyway, the DFT/BS approach based on the hybrid functional B3LYP turns out to be reliable for an accurate prediction of the coupling constant J, not only in binuclear transition metal complexes, 22,23,53 but also in actinide-containing molecules, 19,30 − 35 even though the use of the DFT monodeterminantal approach in such cases is a subject of debate. 9,19,54 Yamaguchi et al 55 have suggested an expression for the correct evaluation of J within the BS approach, which should be valid over the full range of coupling strengths, from the weak to the strong overlapping limit.…”

Section: A Geometry Optimizationsmentioning

confidence: 99%

Electronic structure and magnetic properties of naphthalene- and stilbene-diimide-bridged diuranium(V) complexes: a theoretical study

et al. 2020

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An investigation by DFT of the electronic structure and magnetic properties of a novel μ-oxo-iron(III) complex with the 1,10-phenathroline ligand

Cited by 8 publications

References 66 publications

Electronic Structure and Magneto-Structural Correlations Study of Cu₂UL Trinuclear Schiff Base Complexes: A 3d–5f–3d Case

Electronic Structure and Magneto-Structural Correlations Study of Cu₂UL Trinuclear Schiff Base Complexes: A 3d–5f–3d Case

DFT Investigations of the Magnetic Properties of Actinide Complexes

Electronic structure and magnetic properties of naphthalene- and stilbene-diimide-bridged diuranium(V) complexes: a theoretical study

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An investigation by DFT of the electronic structure and magnetic properties of a novel μ-oxo-iron(III) complex with the 1,10-phenathroline ligand

Cited by 8 publications

References 66 publications

Electronic Structure and Magneto-Structural Correlations Study of Cu2UL Trinuclear Schiff Base Complexes: A 3d–5f–3d Case

Electronic Structure and Magneto-Structural Correlations Study of Cu2UL Trinuclear Schiff Base Complexes: A 3d–5f–3d Case

DFT Investigations of the Magnetic Properties of Actinide Complexes

Electronic structure and magnetic properties of naphthalene- and stilbene-diimide-bridged diuranium(V) complexes: a theoretical study

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Electronic Structure and Magneto-Structural Correlations Study of Cu₂UL Trinuclear Schiff Base Complexes: A 3d–5f–3d Case

Electronic Structure and Magneto-Structural Correlations Study of Cu₂UL Trinuclear Schiff Base Complexes: A 3d–5f–3d Case