A Ferric Semiquinoid Single-Chain Magnet via Thermally-Switchable Metal-Ligand Electron Transfer

Jordan A. Degayner; Kunyu Wang; T. David Harris

doi:10.1021/jacs.8b03949

A Ferric Semiquinoid Single-Chain Magnet via Thermally-Switchable Metal-Ligand Electron Transfer

Jordan A. Degayner, Kunyu Wang, T. David Harris^*

^*Corresponding author for this work

Chemistry

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

77 Scopus citations

Abstract

We report the synthesis of a semiquinoid-bridged single-chain magnet, as generated through a thermally induced metal-ligand electron transfer. Reaction of FeCl₃ with 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone (LH₂) in the presence of (NMe₄)Cl gave the compound (NMe₄)₂[LFeCl₂]. Together, variable-temperature X-ray diffraction, Mössbauer spectra, Raman spectra, and dc magnetic susceptibility reveal a transition from a chain containing (L^2-)Fe^II units to one with (L^3-•)Fe^III upon decreasing temperature, with a transition temperature of T_1/2 = 213 K. The dc magnetic susceptibility measurements show strong metal-radical coupling within the chain, with a coupling constant of J = -81 cm^-1, and ac susceptibility data reveal slow magnetic relaxation, with a relaxation barrier of Δ_τ = 55(1) cm^-1. To our knowledge, this compound provides the first example of a semiquinoid-bridged single-chain magnet.

Original language	English (US)
Pages (from-to)	6550-6553
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	140
Issue number	21
DOIs	https://doi.org/10.1021/jacs.8b03949
State	Published - May 30 2018

ASJC Scopus subject areas

General Chemistry
Biochemistry
Catalysis
Colloid and Surface Chemistry

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10.1021/jacs.8b03949

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title = "A Ferric Semiquinoid Single-Chain Magnet via Thermally-Switchable Metal-Ligand Electron Transfer",

abstract = "We report the synthesis of a semiquinoid-bridged single-chain magnet, as generated through a thermally induced metal-ligand electron transfer. Reaction of FeCl3 with 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone (LH2) in the presence of (NMe4)Cl gave the compound (NMe4)2[LFeCl2]. Together, variable-temperature X-ray diffraction, M{\"o}ssbauer spectra, Raman spectra, and dc magnetic susceptibility reveal a transition from a chain containing (L2-)FeII units to one with (L3-•)FeIII upon decreasing temperature, with a transition temperature of T1/2 = 213 K. The dc magnetic susceptibility measurements show strong metal-radical coupling within the chain, with a coupling constant of J = -81 cm-1, and ac susceptibility data reveal slow magnetic relaxation, with a relaxation barrier of Δτ = 55(1) cm-1. To our knowledge, this compound provides the first example of a semiquinoid-bridged single-chain magnet.",

author = "Degayner, {Jordan A.} and Kunyu Wang and Harris, {T. David}",

note = "Publisher Copyright: {\textcopyright} 2018 American Chemical Society.",

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doi = "10.1021/jacs.8b03949",

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T1 - A Ferric Semiquinoid Single-Chain Magnet via Thermally-Switchable Metal-Ligand Electron Transfer

AU - Degayner, Jordan A.

AU - Wang, Kunyu

AU - Harris, T. David

PY - 2018/5/30

Y1 - 2018/5/30

N2 - We report the synthesis of a semiquinoid-bridged single-chain magnet, as generated through a thermally induced metal-ligand electron transfer. Reaction of FeCl3 with 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone (LH2) in the presence of (NMe4)Cl gave the compound (NMe4)2[LFeCl2]. Together, variable-temperature X-ray diffraction, Mössbauer spectra, Raman spectra, and dc magnetic susceptibility reveal a transition from a chain containing (L2-)FeII units to one with (L3-•)FeIII upon decreasing temperature, with a transition temperature of T1/2 = 213 K. The dc magnetic susceptibility measurements show strong metal-radical coupling within the chain, with a coupling constant of J = -81 cm-1, and ac susceptibility data reveal slow magnetic relaxation, with a relaxation barrier of Δτ = 55(1) cm-1. To our knowledge, this compound provides the first example of a semiquinoid-bridged single-chain magnet.

AB - We report the synthesis of a semiquinoid-bridged single-chain magnet, as generated through a thermally induced metal-ligand electron transfer. Reaction of FeCl3 with 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone (LH2) in the presence of (NMe4)Cl gave the compound (NMe4)2[LFeCl2]. Together, variable-temperature X-ray diffraction, Mössbauer spectra, Raman spectra, and dc magnetic susceptibility reveal a transition from a chain containing (L2-)FeII units to one with (L3-•)FeIII upon decreasing temperature, with a transition temperature of T1/2 = 213 K. The dc magnetic susceptibility measurements show strong metal-radical coupling within the chain, with a coupling constant of J = -81 cm-1, and ac susceptibility data reveal slow magnetic relaxation, with a relaxation barrier of Δτ = 55(1) cm-1. To our knowledge, this compound provides the first example of a semiquinoid-bridged single-chain magnet.

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A Ferric Semiquinoid Single-Chain Magnet via Thermally-Switchable Metal-Ligand Electron Transfer

Abstract

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CCDC 1847320: Experimental Crystal Structure Determination

CCDC 1847321: Experimental Crystal Structure Determination

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A Ferric Semiquinoid Single-Chain Magnet via Thermally-Switchable Metal-Ligand Electron Transfer

Abstract

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CCDC 1847320: Experimental Crystal Structure Determination

CCDC 1847321: Experimental Crystal Structure Determination

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