Crystal Field in Rare‐Earth Complexes: From Electrostatics to Bonding

Alessandri, Riccardo; Zulfikri, Habiburrahman; Autschbach, Jochen; Bolvin, Hélène

doi:10.1002/chem.201705748

Cited by 26 publications

(47 citation statements)

References 83 publications

(155 reference statements)

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“…This work completes a previous study in which another question about CFPs was addressed, namely the transferability of the CFPs from the orbital picture to the many‐electron picture, including spin–orbit coupling. It emerged from this previous study that covalent effects between the metal and the ligands affect the CFPs, even for the ionic PrCl 3 crystal . This will be confirmed by the present work in which we aimed to address the following points: 1) Do the two above‐mentioned methods provide similar CFPs?…”

Section: Introductionsupporting

confidence: 71%

“…As discussed in Ref. ,

α_{J}^{2}

changes sign between holmium and erbium. This impacts the ordering of the states in terms of | M J |: For terbium and dysprosium, | M J | increases with the energy, for ytterbium, it decreases.…”

Section: Resultsmentioning

confidence: 66%

“…

B_{0}^{2}

is the largest in magnitude, and negative as expected from a compressed environment. This negative value of

B_{0}^{2}

leads the magnetization to be axial in the erbium derivative, and planar in the dysprosium derivative .

B_{0}^{4}

and

B_{0}^{6}

are far from non‐negligible, around ±500 cm −1 , and opposite in sign, which leads to entangled spectra in terms of | M J |.…”

Section: Resultsmentioning

confidence: 99%

“…Because the incorporation of some covalency keeps the one‐electron structure,

{\overset{V}{true}}^{CF}

may be seen as an effective interaction, the parameters of which are fitted on experimental data. We showed in a recent article that the CFPs deduced from orbital energies ( X = l ) and from many‐electron wave functions without or with spin–orbit coupling ( X = L and J , respectively) lead to similar CFPs. Consequently, the reduced elements

α_{X}^{k}

depend on the nature of the metal, and the CFPs

B_{q}^{k}

only on the nature and position of the ligands, and should be transferable within the lanthanide series.…”

Section: Introductionmentioning

confidence: 86%

“…This method was applied to the LnZn 16 series, which evidence a symmetry very close to D 4 d . This is still feasible when a few off‐diagonal terms are present ( q ≠0), as for D 3 h with an additional

B_{6}^{6}

term …”

Section: Introductionmentioning

confidence: 99%

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Derivation of Lanthanide Series Crystal Field Parameters From First Principles

Jung

Islam

Pecoraro

et al. 2019

Chemistry A European J

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Two series of lanthanide complexes have been chosen to analyze trends in the magnetic properties and crystal field parameters (CFPs) along the two series: The highly symmetric LnZn16(picHA)16 series (Ln=Tb, Dy, Ho, Er, Yb; picHA=picolinohydroxamic acid) and the [Ln(dpa)3](C3H5N2)3⋅3H2O series (Ln=Ce–Yb; dpa=2,6‐dipicolinic acid) with approximate three‐fold symmetry. The first series presents a compressed coordination sphere of eight oxygen atoms whereas in the second series, the coordination sphere consists of an elongated coordination sphere formed of six oxygen atoms. The CFPs have been deduced from ab initio calculations using two methods: The AILFT (ab initio ligand field theory) method, in which the parameters are determined at the orbital level, and the ITO (irreducible tensor operator) decomposition, in which the problems are treated at the many‐electron level. It has been found that the CFPs are transferable from one derivative to another, within a given series, as a first approximation. The sign of the second‐order parameter B02 differs in the two series, reflecting the different environments. It has been found that the use of the strength parameter S allows for an easy comparison between complexes. Furthermore, in both series, the parameters have been found to decrease in magnitude along the series, and this decrease is attributed to covalent effects.

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Section: Introductionsupporting

confidence: 71%

“…As discussed in Ref. ,

α_{J}^{2}

changes sign between holmium and erbium. This impacts the ordering of the states in terms of | M J |: For terbium and dysprosium, | M J | increases with the energy, for ytterbium, it decreases.…”

Section: Resultsmentioning

confidence: 66%

“…

B_{0}^{2}

is the largest in magnitude, and negative as expected from a compressed environment. This negative value of

B_{0}^{2}

leads the magnetization to be axial in the erbium derivative, and planar in the dysprosium derivative .

B_{0}^{4}

and

B_{0}^{6}

are far from non‐negligible, around ±500 cm −1 , and opposite in sign, which leads to entangled spectra in terms of | M J |.…”

Section: Resultsmentioning

confidence: 99%

“…Because the incorporation of some covalency keeps the one‐electron structure,

{\overset{V}{true}}^{CF}

α_{X}^{k}

depend on the nature of the metal, and the CFPs

B_{q}^{k}

only on the nature and position of the ligands, and should be transferable within the lanthanide series.…”

Section: Introductionmentioning

confidence: 86%

B_{6}^{6}

term …”

Section: Introductionmentioning

confidence: 99%

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Derivation of Lanthanide Series Crystal Field Parameters From First Principles

Jung

Islam

Pecoraro

et al. 2019

Chemistry A European J

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Dysprosiacarboranes as Organometallic Single‐Molecule Magnets

Jin

Zhai

et al. 2020

Angewandte Chemie

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The dicarbollide ion, nido‐C2B9H112− is isoelectronic with cyclopentadienyl. Herein, we make dysprosiacarboranes, namely [(C2B9H11)2Ln(THF)2][Na(THF)5] (Ln=Dy, 1Dy) and [(THF)3(μ‐H)3Li]2[{η5‐C6H4(CH2)2C2B9H9}Dy{η2:η5‐C6H4(CH2)2C2B9H9}2Li] 3Dy and show that dicarbollide ligands impose strong magnetic axiality on the central DyIII ion. The effective energy barrier (Ueff) for the loss of magnetization can be varied by the substitution pattern on the dicarbollide. This finding is demonstrated by comparing complexes of nido‐C2B9H112− and nido‐[o‐xylylene‐C2B9H9]2−, which show a Ueff of 430(5) K and 804(7) K, respectively. The blocking temperature defined by the open hysteresis temperature of 3Dy reaches 6.8 K. Moreover, the linear complex [Dy(C2B9H11)2]− is predicted to have comparable properties with the linear [Dy(CpMe3)2]+ complex. As such, carboranyl ligands and their derivatives may provide a new type of organometallic ligand for high‐performance single‐molecule magnets.

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