Determination of the electronic structure of a dinuclear dysprosium single molecule magnet without symmetry idealization

Mauro Perfetti; Maren Gysler; Yvonne Rechkemmer-Patalen; Peng Zhang; Hatice Taştan; Florian Fischer; Julia Netz; Wolfgang Frey; Lucas W. Zimmermann; Thomas Schleid; Michael Hakl; Milan Orlita; Liviu Ungur; Liviu Chibotaru; Theis Brock-Nannestad; Stergios Piligkos; Joris Van Slageren

doi:10.1039/C8SC03170C

Determination of the electronic structure of a dinuclear dysprosium single molecule magnet without symmetry idealization

Mauro Perfetti, Maren Gysler, Yvonne Rechkemmer-Patalen, Peng Zhang, Hatice Taştan, Florian Fischer, Julia Netz, Wolfgang Frey, Lucas W. Zimmermann, Thomas Schleid, Michael Hakl, Milan Orlita, Liviu Ungur, Liviu Chibotaru, Theis Brock-Nannestad, Stergios Piligkos, Joris Van Slageren^*

^*Corresponding author for this work

Department of Chemistry

24 Citations (Scopus)

Abstract

We present the in-depth determination of the magnetic properties and electronic structure of the luminescent and volatile dysprosium-based single molecule magnet [Dy ₂ (bpm)(fod) ₆ ] (Hfod = 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione, bpm = 2,2′-bipyrimidine). Ab initio calculations were used to obtain a global picture of the electronic structure and to predict possible single molecule magnet behaviour, confirmed by experiments. The orientation of the susceptibility tensor was determined by means of cantilever torque magnetometry. An experimental determination of the electronic structure of the lanthanide ion was obtained combining Luminescence, Far Infrared and Magnetic Circular Dichroism spectroscopies. Fitting these energies to the full single ion plus crystal field Hamiltonian allowed determination of the eigenstates and crystal field parameters of a lanthanide complex without symmetry idealization. We then discuss the impact of a stepwise symmetry idealization on the modelling of the experimental data. This result is particularly important in view of the misleading outcomes that are often obtained when the symmetry of lanthanide complexes is idealized.

Original language	English
Journal	Chemical Science
Volume	10
Issue number	7
Pages (from-to)	2101-2110
Number of pages	10
ISSN	2041-6520
DOIs	https://doi.org/10.1039/C8SC03170C
Publication status	Published - 2019

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10.1039/C8SC03170C

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Perfetti, M., Gysler, M., Rechkemmer-Patalen, Y., Zhang, P., Taştan, H., Fischer, F., Netz, J., Frey, W., Zimmermann, L. W., Schleid, T., Hakl, M., Orlita, M., Ungur, L., Chibotaru, L., Brock-Nannestad, T., Piligkos, S., & Van Slageren, J. (2019). Determination of the electronic structure of a dinuclear dysprosium single molecule magnet without symmetry idealization. Chemical Science, 10(7), 2101-2110. https://doi.org/10.1039/C8SC03170C

Perfetti, M, Gysler, M, Rechkemmer-Patalen, Y, Zhang, P, Taştan, H, Fischer, F, Netz, J, Frey, W, Zimmermann, LW, Schleid, T, Hakl, M, Orlita, M, Ungur, L, Chibotaru, L, Brock-Nannestad, T , Piligkos, S & Van Slageren, J 2019, 'Determination of the electronic structure of a dinuclear dysprosium single molecule magnet without symmetry idealization', Chemical Science, vol. 10, no. 7, pp. 2101-2110. https://doi.org/10.1039/C8SC03170C

@article{e5e27d7961d040a3a2339da880586514,

title = "Determination of the electronic structure of a dinuclear dysprosium single molecule magnet without symmetry idealization",

abstract = " We present the in-depth determination of the magnetic properties and electronic structure of the luminescent and volatile dysprosium-based single molecule magnet [Dy 2 (bpm)(fod) 6 ] (Hfod = 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione, bpm = 2,2′-bipyrimidine). Ab initio calculations were used to obtain a global picture of the electronic structure and to predict possible single molecule magnet behaviour, confirmed by experiments. The orientation of the susceptibility tensor was determined by means of cantilever torque magnetometry. An experimental determination of the electronic structure of the lanthanide ion was obtained combining Luminescence, Far Infrared and Magnetic Circular Dichroism spectroscopies. Fitting these energies to the full single ion plus crystal field Hamiltonian allowed determination of the eigenstates and crystal field parameters of a lanthanide complex without symmetry idealization. We then discuss the impact of a stepwise symmetry idealization on the modelling of the experimental data. This result is particularly important in view of the misleading outcomes that are often obtained when the symmetry of lanthanide complexes is idealized. ",

author = "Mauro Perfetti and Maren Gysler and Yvonne Rechkemmer-Patalen and Peng Zhang and Hatice Ta{\c s}tan and Florian Fischer and Julia Netz and Wolfgang Frey and Zimmermann, {Lucas W.} and Thomas Schleid and Michael Hakl and Milan Orlita and Liviu Ungur and Liviu Chibotaru and Theis Brock-Nannestad and Stergios Piligkos and {Van Slageren}, Joris",

note = "Correction: https://doi.org/10.1039/C9SC90051A",

year = "2019",

doi = "10.1039/C8SC03170C",

language = "English",

volume = "10",

pages = "2101--2110",

journal = "Chemical Science",

issn = "2041-6520",

publisher = "Royal Society of Chemistry",

number = "7",

}

TY - JOUR

T1 - Determination of the electronic structure of a dinuclear dysprosium single molecule magnet without symmetry idealization

AU - Perfetti, Mauro

AU - Gysler, Maren

AU - Rechkemmer-Patalen, Yvonne

AU - Zhang, Peng

AU - Taştan, Hatice

AU - Fischer, Florian

AU - Netz, Julia

AU - Frey, Wolfgang

AU - Zimmermann, Lucas W.

AU - Schleid, Thomas

AU - Hakl, Michael

AU - Orlita, Milan

AU - Ungur, Liviu

AU - Chibotaru, Liviu

AU - Brock-Nannestad, Theis

AU - Piligkos, Stergios

AU - Van Slageren, Joris

N1 - Correction: https://doi.org/10.1039/C9SC90051A

PY - 2019

Y1 - 2019

N2 - We present the in-depth determination of the magnetic properties and electronic structure of the luminescent and volatile dysprosium-based single molecule magnet [Dy 2 (bpm)(fod) 6 ] (Hfod = 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione, bpm = 2,2′-bipyrimidine). Ab initio calculations were used to obtain a global picture of the electronic structure and to predict possible single molecule magnet behaviour, confirmed by experiments. The orientation of the susceptibility tensor was determined by means of cantilever torque magnetometry. An experimental determination of the electronic structure of the lanthanide ion was obtained combining Luminescence, Far Infrared and Magnetic Circular Dichroism spectroscopies. Fitting these energies to the full single ion plus crystal field Hamiltonian allowed determination of the eigenstates and crystal field parameters of a lanthanide complex without symmetry idealization. We then discuss the impact of a stepwise symmetry idealization on the modelling of the experimental data. This result is particularly important in view of the misleading outcomes that are often obtained when the symmetry of lanthanide complexes is idealized.

AB - We present the in-depth determination of the magnetic properties and electronic structure of the luminescent and volatile dysprosium-based single molecule magnet [Dy 2 (bpm)(fod) 6 ] (Hfod = 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione, bpm = 2,2′-bipyrimidine). Ab initio calculations were used to obtain a global picture of the electronic structure and to predict possible single molecule magnet behaviour, confirmed by experiments. The orientation of the susceptibility tensor was determined by means of cantilever torque magnetometry. An experimental determination of the electronic structure of the lanthanide ion was obtained combining Luminescence, Far Infrared and Magnetic Circular Dichroism spectroscopies. Fitting these energies to the full single ion plus crystal field Hamiltonian allowed determination of the eigenstates and crystal field parameters of a lanthanide complex without symmetry idealization. We then discuss the impact of a stepwise symmetry idealization on the modelling of the experimental data. This result is particularly important in view of the misleading outcomes that are often obtained when the symmetry of lanthanide complexes is idealized.

U2 - 10.1039/C8SC03170C

DO - 10.1039/C8SC03170C

M3 - Journal article

AN - SCOPUS:85061600351

SN - 2041-6520

VL - 10

SP - 2101

EP - 2110

JO - Chemical Science

JF - Chemical Science

IS - 7

ER -

Determination of the electronic structure of a dinuclear dysprosium single molecule magnet without symmetry idealization

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