A Linear Dysprosium(II) Metallocene with a High Effective Energy Barrier and Magnetic Hysteresis up to 70 Kelvin DOI Creative Commons
Ming Liu, Yan‐Cong Chen, Huan Wang

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: May 14, 2025

Dysprosium in the oxidation state +3 is ubiquitous studies of single-molecule magnets (SMMs). In contrast, SMMs based on lanthanides +2 are rare, and examples with both a high effective energy barrier to reversal magnetization hysteresis coercivity at temperatures extremely uncommon. Here, we show that one-electron reduction dysprosium(III) complex [(η5-C5iPr5)Dy(η5-Cp*)(BH4)] (Cp* = C5Me5) KC8 generates linear dysprosium(II) metallocene [(η5-C5iPr5)Dy(η5-Cp*)]. Magnetic measurements, ultraviolet/visible/near infrared (UV/vis/NIR) spectroscopy theoretical calculations center [(η5-C5iPr5)Dy(η5-Cp*)] adopts 4f9 (6s/5d)1 configuration. Coupling 4f 5d electrons results an magnetic moment 11.38 μB 217 K, equaling highest recorded for mononuclear complex. AC DC measurements establish SMM properties [(η5-C5iPr5)Dy(η5-Cp*)], including 1551 cm-1, largest yet reported divalent lanthanide SMM, 100-s blocking temperature 62 K. produce loops remain open up 70 Multireference reveal easy-axis ground doublet coincides molecular symmetry axis, this has strong axial character. The axiality Orbach relaxation probably occurring via second-excited doublet. parameters insight suggest linked perfectly crystal field experienced by center.

Language: Английский

A Linear Dysprosium(II) Metallocene with a High Effective Energy Barrier and Magnetic Hysteresis up to 70 Kelvin DOI Creative Commons
Ming Liu, Yan‐Cong Chen, Huan Wang

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: May 14, 2025

Dysprosium in the oxidation state +3 is ubiquitous studies of single-molecule magnets (SMMs). In contrast, SMMs based on lanthanides +2 are rare, and examples with both a high effective energy barrier to reversal magnetization hysteresis coercivity at temperatures extremely uncommon. Here, we show that one-electron reduction dysprosium(III) complex [(η5-C5iPr5)Dy(η5-Cp*)(BH4)] (Cp* = C5Me5) KC8 generates linear dysprosium(II) metallocene [(η5-C5iPr5)Dy(η5-Cp*)]. Magnetic measurements, ultraviolet/visible/near infrared (UV/vis/NIR) spectroscopy theoretical calculations center [(η5-C5iPr5)Dy(η5-Cp*)] adopts 4f9 (6s/5d)1 configuration. Coupling 4f 5d electrons results an magnetic moment 11.38 μB 217 K, equaling highest recorded for mononuclear complex. AC DC measurements establish SMM properties [(η5-C5iPr5)Dy(η5-Cp*)], including 1551 cm-1, largest yet reported divalent lanthanide SMM, 100-s blocking temperature 62 K. produce loops remain open up 70 Multireference reveal easy-axis ground doublet coincides molecular symmetry axis, this has strong axial character. The axiality Orbach relaxation probably occurring via second-excited doublet. parameters insight suggest linked perfectly crystal field experienced by center.

Language: Английский

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