Comprehensive insight into molecular magnetism via CONDON: Full vs. effective models

Leusen, Jan van; Speldrich, Manfred; Schilder, Helmut; Kögerler, Paul

doi:10.1016/j.ccr.2014.10.011

Cited by 75 publications

(54 citation statements)

References 44 publications

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“…NMR spectra were recorded in C 6 D 6 using a Jeol FX-90Q spectrometer. The data are also corrected for the overall diamagnetism of the molecule using Pascal constants Crystal field model (CONDON) 34 To analyze the magnetic characteristics of the title compounds, we focus on the splitting and mixing of the relevant multiplet energy levels, mainly those of 4 I 9/2 and 4 I 11/2 for these f 3 complexes, considering all relevant interactions. The low temperature EPR spectra were fit using a version of the code ABVG 38 modified to fit spectra in the frequency regime as suggested by Pilbrow 39 and to fit spectra using the downhill simplex method.…”

Section: Physical Measurementsmentioning

confidence: 99%

“…Like Cp 3 Nd, Cp 3 U has three unpaired f electrons, and magnetic measurements can provide information about its electronic structure. 34 The electronic structures of (1-6) were also determined computationally by density functional theory (DFT) and multireference wavefunction calcuations. 25 While spectroscopic studies of Cp 3 U electronic structure are few, this system has been studied computationally starting with an MO description of the bonding in the Cp 3 U + fragment.…”

Section: Introductionmentioning

confidence: 99%

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The roles of 4f- and 5f-orbitals in bonding: a magnetochemical, crystal field, density functional theory, and multi-reference wavefunction study

et al. 2016

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The electronic structures of 4f(3)/5f(3) Cp''3M and Cp''3M·alkylisocyanide complexes, where Cp'' is 1,3-bis-(trimethylsilyl)cyclopentadienyl, are explored with a focus on the splitting of the f-orbitals, which provides information about the strengths of the metal-ligand interactions. While the f-orbital splitting in many lanthanide complexes has been reported in detail, experimental determination of the f-orbital splitting in actinide complexes remains rare in systems other than halide and oxide compounds, since the experimental approach, crystal field analysis, is generally significantly more difficult for actinide complexes than for lanthanide complexes. In this study, a set of analogous neodymium(iii) and uranium(iii) tris-cyclopentadienyl complexes and their isocyanide adducts was characterized by electron paramagnetic resonance (EPR) spectroscopy and magnetic susceptibility. The crystal field model was parameterized by combined fitting of EPR and susceptibility data, yielding an accurate description of f-orbital splitting. The isocyanide derivatives were also studied using density functional theory, resulting in f-orbital splitting that is consistent with crystal field fitting, and by multi-reference wavefunction calculations that support the electronic structure analysis derived from the crystal-field calculations. The results highlight that the 5f-orbitals, but not the 4f-orbitals, are significantly involved in bonding to the isocyanide ligands. The main interaction between isocyanide ligand and the metal center is a σ-bond, with additional 5f to π* donation for the uranium complexes. While interaction with the isocyanide π*-orbitals lowers the energies of the 5fxz(2) and 5fyz(2)-orbitals, spin-orbit coupling greatly reduces the population of 5fxz(2) and 5fyz(2) in the ground state.

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Section: Physical Measurementsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

The roles of 4f- and 5f-orbitals in bonding: a magnetochemical, crystal field, density functional theory, and multi-reference wavefunction study

et al. 2016

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“…[4a,b] The magnetic properties of SMMsa re related to the electronics tructure of the metal site and therefore to the molecular structure. [6] Apart from magnetic studies, which only provide for qualitative/semi-quantitativec orrelations, rigorous validationo ft hese computational methods is rarely reported. [5] This has become as tandard procedure, although it is not withoutc riticism.…”

Section: Introductionmentioning

confidence: 99%

Correlation of Structural and Magnetic Properties in a Set of Mononuclear Lanthanide Complexes

Comba

Daumann

Klingeler

et al. 2018

Chemistry A European J

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The electronic and magnetic properties of a set of mononuclear terbium(III) and dysprosium(III) complexes with two tetradentate 1-hydroxy-pyridin-2-one (1,2-HOPO) ligands are reported. Two primary coordination geometries are observed, depending on the length of the linker between the 1,2-HOPO donor moieties and the resulting arrangements of the linker. Fine details of the magnetic circular dichroism (MCD) spectra of the dysprosium(III) complexes illustrate differences in the splitting of the J multiplets and allow for a thorough ligand field analysis. High frequency electron paramagnetic resonance (HF-EPR) studies of the terbium(III) complexes give insight into the composition of the ground states. Ab initio calculations are utilized to rationalize the experimental results and further illustrate the effect of the structural features on the electronic and magnetic properties of the different complexes.

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“…The program CONDON [67][68][69] allows for a treatment of the full Hilbert space of all possible microstates of the 4f shell and outputs magnetic properties such as magnetic susceptibility and field-dependent magnetization. Similarly, the recently developed software SIMPRE [70] is able to calculate magnetic properties of SIMs from sets of Stevens parameters, and it works with effective point-charge models which can provide a more intuitive insight than full ab initio calulcations.…”

Section: Determination Of Ligand-field Parametersmentioning

confidence: 99%

Molecular lanthanide single-ion magnets: from bulk to submonolayers

Dreiser¹

2015

J. Phys.: Condens. Matter

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Single-ion magnets (SIMs) are mononuclear molecular complexes exhibiting slow relaxation of magnetization. They are currently attracting a lot of interest because of potential applications in spintronics and quantum information processing. However, exploiting SIMs in, e.g. molecule-inorganic hybrid devices requires a fundamental understanding of the effects of molecule-substrate interactions on the SIM magnetic properties. In this review the properties of lanthanide SIMs in the bulk crystalline phase and deposited on surfaces in the (sub)monolayer regime are discussed. As a starting point trivalent lanthanide ions in a ligand field will be described, and the challenges in characterizing the ligand field are illustrated with a focus on several spectroscopic techniques which are able to give direct information on the ligand-field split energy levels. Moreover, the dominant mechanisms of magnetization relaxation in the bulk phase are discussed followed by an overview of SIMs relevant for surface deposition. Further, a short introduction will be given on x-ray absorption spectroscopy, x-ray magnetic circular dichroism and scanning tunneling microscopy. Finally, the recent experiments on surface-deposited SIMs will be reviewed, along with a discussion of future perspectives.

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Comprehensive insight into molecular magnetism via CONDON: Full vs. effective models

Cited by 75 publications

References 44 publications

The roles of 4f- and 5f-orbitals in bonding: a magnetochemical, crystal field, density functional theory, and multi-reference wavefunction study

The roles of 4f- and 5f-orbitals in bonding: a magnetochemical, crystal field, density functional theory, and multi-reference wavefunction study

Correlation of Structural and Magnetic Properties in a Set of Mononuclear Lanthanide Complexes

Molecular lanthanide single-ion magnets: from bulk to submonolayers

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