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A Ferric Semiquinoid Single-Chain Magnet via Thermally-Switchable Metal-Ligand Electron Transfer
Jordan A DeGayner1, Kunyu Wang1, T David Harris1
1Department of Chemistry , Northwestern University , Evanston , Illinois 60208-3313 , United States.
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 (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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