Radical-Bridged Heterometallic Single-Molecule Magnets Incorporating Four Lanthanoceniums

Peng Zhang; Qian Cheng Luo; Zhenhua Zhu; Wanrong He; Nan Song; Junting Lv; Xuning Wang; Quan Guo Zhai; Yan Zhen Zheng; Jinkui Tang

doi:10.1002/anie.202218540

Radical-Bridged Heterometallic Single-Molecule Magnets Incorporating Four Lanthanoceniums

Peng Zhang
, Qian Cheng Luo
, Zhenhua Zhu
, Wanrong He
, Nan Song
, Junting Lv
, Xuning Wang
, Quan Guo Zhai
, Yan Zhen Zheng
, Jinkui Tang

School of Materials Science and Engineering

Research output: Contribution to journal › Article › peer-review

51 Scopus citations

Abstract

The syntheses and magnetic properties of organometallic heterometallic compounds [K(THF)₆]{Co^I[(μ₃-HAN)RE₂Cp*₄]₂} (1-RE) and [K(Crypt)]₂{Co^I[(μ₃-HAN)RE₂Cp*₄]₂} (2-RE) containing hexaazatrinaphthylene radicals (HAN⋅³⁻) and four rare earth (RE) ions are reported. 1-RE shows isolable species with ligand-based mixed valency as revealed by cyclic voltammetry (CV) thus leading to the isolation of 2-RE via one-electron chemical reduction. Strong electronic communication in mixed-valency supports stronger overall ferromagnetic behaviors in 2-RE than 1-RE containing Gd and Dy ions. Ac magnetic susceptibility data reveal 1-Dy and 2-Dy both exhibit slow magnetic relaxation. Importantly, larger coercive field was observed in the hysteresis of 2-Dy at 2.0 K, indicating the enhanced SMM behavior compared with 1-Dy. Ligand-based mixed-valency strategy has been used for the first time to improve the magnetic coupling in lanthanide (Ln) SMMs, thus opening up new ways to construct strongly coupled Ln-SMMs.

Original language	English
Article number	e202218540
Journal	Angewandte Chemie - International Edition
Volume	62
Issue number	12
DOIs	https://doi.org/10.1002/anie.202218540
State	Published - 13 Mar 2023

Keywords

Heterometallic
Lanthanide
Mixed Valence
Radical Bridge
Single Molecule Magnets

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10.1002/anie.202218540

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@article{188f232ec4f640c8aaedc56e2577a107,

title = "Radical-Bridged Heterometallic Single-Molecule Magnets Incorporating Four Lanthanoceniums",

abstract = "The syntheses and magnetic properties of organometallic heterometallic compounds [K(THF)6]\{CoI[(μ3-HAN)RE2Cp*4]2\} (1-RE) and [K(Crypt)]2\{CoI[(μ3-HAN)RE2Cp*4]2\} (2-RE) containing hexaazatrinaphthylene radicals (HAN⋅3−) and four rare earth (RE) ions are reported. 1-RE shows isolable species with ligand-based mixed valency as revealed by cyclic voltammetry (CV) thus leading to the isolation of 2-RE via one-electron chemical reduction. Strong electronic communication in mixed-valency supports stronger overall ferromagnetic behaviors in 2-RE than 1-RE containing Gd and Dy ions. Ac magnetic susceptibility data reveal 1-Dy and 2-Dy both exhibit slow magnetic relaxation. Importantly, larger coercive field was observed in the hysteresis of 2-Dy at 2.0 K, indicating the enhanced SMM behavior compared with 1-Dy. Ligand-based mixed-valency strategy has been used for the first time to improve the magnetic coupling in lanthanide (Ln) SMMs, thus opening up new ways to construct strongly coupled Ln-SMMs.",

keywords = "Heterometallic, Lanthanide, Mixed Valence, Radical Bridge, Single Molecule Magnets",

author = "Peng Zhang and Luo, \{Qian Cheng\} and Zhenhua Zhu and Wanrong He and Nan Song and Junting Lv and Xuning Wang and Zhai, \{Quan Guo\} and Zheng, \{Yan Zhen\} and Jinkui Tang",

note = "Publisher Copyright: {\textcopyright} 2023 Wiley-VCH GmbH.",

year = "2023",

month = mar,

day = "13",

doi = "10.1002/anie.202218540",

language = "英语",

volume = "62",

journal = "Angewandte Chemie - International Edition",

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publisher = "John Wiley and Sons Ltd",

number = "12",

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TY - JOUR

T1 - Radical-Bridged Heterometallic Single-Molecule Magnets Incorporating Four Lanthanoceniums

AU - Zhang, Peng

AU - Luo, Qian Cheng

AU - Zhu, Zhenhua

AU - He, Wanrong

AU - Song, Nan

AU - Lv, Junting

AU - Wang, Xuning

AU - Zhai, Quan Guo

AU - Zheng, Yan Zhen

AU - Tang, Jinkui

PY - 2023/3/13

Y1 - 2023/3/13

N2 - The syntheses and magnetic properties of organometallic heterometallic compounds [K(THF)6]{CoI[(μ3-HAN)RE2Cp*4]2} (1-RE) and [K(Crypt)]2{CoI[(μ3-HAN)RE2Cp*4]2} (2-RE) containing hexaazatrinaphthylene radicals (HAN⋅3−) and four rare earth (RE) ions are reported. 1-RE shows isolable species with ligand-based mixed valency as revealed by cyclic voltammetry (CV) thus leading to the isolation of 2-RE via one-electron chemical reduction. Strong electronic communication in mixed-valency supports stronger overall ferromagnetic behaviors in 2-RE than 1-RE containing Gd and Dy ions. Ac magnetic susceptibility data reveal 1-Dy and 2-Dy both exhibit slow magnetic relaxation. Importantly, larger coercive field was observed in the hysteresis of 2-Dy at 2.0 K, indicating the enhanced SMM behavior compared with 1-Dy. Ligand-based mixed-valency strategy has been used for the first time to improve the magnetic coupling in lanthanide (Ln) SMMs, thus opening up new ways to construct strongly coupled Ln-SMMs.

AB - The syntheses and magnetic properties of organometallic heterometallic compounds [K(THF)6]{CoI[(μ3-HAN)RE2Cp*4]2} (1-RE) and [K(Crypt)]2{CoI[(μ3-HAN)RE2Cp*4]2} (2-RE) containing hexaazatrinaphthylene radicals (HAN⋅3−) and four rare earth (RE) ions are reported. 1-RE shows isolable species with ligand-based mixed valency as revealed by cyclic voltammetry (CV) thus leading to the isolation of 2-RE via one-electron chemical reduction. Strong electronic communication in mixed-valency supports stronger overall ferromagnetic behaviors in 2-RE than 1-RE containing Gd and Dy ions. Ac magnetic susceptibility data reveal 1-Dy and 2-Dy both exhibit slow magnetic relaxation. Importantly, larger coercive field was observed in the hysteresis of 2-Dy at 2.0 K, indicating the enhanced SMM behavior compared with 1-Dy. Ligand-based mixed-valency strategy has been used for the first time to improve the magnetic coupling in lanthanide (Ln) SMMs, thus opening up new ways to construct strongly coupled Ln-SMMs.

KW - Heterometallic

KW - Lanthanide

KW - Mixed Valence

KW - Radical Bridge

KW - Single Molecule Magnets

UR - https://www.scopus.com/pages/publications/85147910076

U2 - 10.1002/anie.202218540

DO - 10.1002/anie.202218540

M3 - 文章

C2 - 36710242

AN - SCOPUS:85147910076

SN - 1433-7851

VL - 62

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 12

M1 - e202218540

ER -

Radical-Bridged Heterometallic Single-Molecule Magnets Incorporating Four Lanthanoceniums

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Keywords

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