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• W2300887109 startingPage "2235" @default.
• W2300887109 abstract "The one-electron reduction of ((tbs)L)Fe₃(thf)¹ furnishes [M][((tbs)L)Fe₃] ([M]⁺ = [(18-C-6)K(thf)₂]⁺ (1, 76%) or [(crypt-222)K]⁺ (2, 54%)). Upon reduction, the ligand (tbs)L⁶⁻ rearranges around the triiron core to adopt an almost ideal C₃-symmetry. Accompanying the ((tbs)L) ligand rearrangement, the THF bound to the neutral starting material is expelled, and the Fe-Fe distances within the trinuclear cluster contract by ∼0.13 Å in 1. Variable-temperature magnetic susceptibility data indicates a well-isolated S = 11/2 spin ground state that persists to room temperature. Slow magnetic relaxation is observed at low temperature as evidenced by the out-of-phase (χ(M)″) component of the alternating current (ac) magnetic susceptibility data and by the appearance of hyperfine splitting in the zero-field ⁵⁷Fe Mössbauer spectra at 4.2 K. Analysis of the ac magnetic susceptibility yields an effective spin reversal barrier (U(eff)) of 22.6(2) cm⁻¹, nearly matching the theoretical barrier of 38.7 cm⁻¹ calculated from the axial zero-field splitting parameter (D = -1.29 cm⁻¹) extracted from the reduced magnetization data. A polycrystalline sample of 1 displays three sextets in the Mössbauer spectrum at 4.2 K (H(ext) = 0) which converge to a single six-line pattern in a frozen 2-MeTHF glass sample, indicating a unique iron environment and thus strong electron delocalization. The spin ground state and ligand rearrangement are discussed within the framework of a fully delocalized cluster exhibiting strong double and direct exchange interactions." @default.
• W2300887109 created "2016-06-24" @default.
• W2300887109 creator A5022569799 @default.
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• W2300887109 creator A5068432879 @default.
• W2300887109 date "2016-02-09" @default.
• W2300887109 modified "2023-10-12" @default.
• W2300887109 title "Maximizing Electron Exchange in a [Fe₃] Cluster" @default.
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• W2300887109 doi "https://doi.org/10.1021/jacs.5b12181" @default.
• W2300887109 hasPubMedCentralId "https://www.ncbi.nlm.nih.gov/pmc/articles/5567842" @default.
• W2300887109 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/26799500" @default.
• W2300887109 hasPublicationYear "2016" @default.
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