Abstract

The magnetic, electronic, and Mössbauer spectral properties of Fe 2L(µ-OAc)2ClO4, 1, where L is the dianion of the tetraimino-diphenolate macrocyclic ligand, H2L, indicate that 1 is a class III mixed valence iron(II/III) complex with an electron that is fully delocalized between two crystallographically inequivalent iron sites to yield a [Fe2]V cationic configuration with a St 9/2 ground state. Fits of the dc magnetic susceptibility between 2 and 300K and of the isofield variable-temperature magnetization of 1 yield an isotropic magnetic exchange parameter, J, of -32(2) cm-1 for an electron transfer parameter, B, of 950 cm-1, a zero-field uniaxial D9/2 parameter of -0.9(1) cm-1, and g 1.95(5). In agreement with the presence of uniaxial magnetic anisotropy, ac susceptibility measurements reveal that 1 is a single-molecule magnet at low temperature with a single molecule magnetic effective relaxation barrier, Ueff, of 9.8 cm-1. At 5.25 K the Mössbauer spectra of 1 exhibit two spectral components, assigned to the two crystallographically inequivalent iron sites with a static effective hyperfine field; as the temperature increases from 7 to 310 K, the spectra exhibit increasingly rapid relaxation of the hyperfine field on the iron-57 Larmor precession time of 5 x 10-8 s. A fit of the temperature dependence of the average effective hyperfine field yields |D9/2| 0.9 cm-1. An Arrhenius plot of the logarithm of the relaxation frequency between 5 and 85 K yields a relaxation barrier of 17 cm-1.

Department(s)

Chemistry

Keywords and Phrases

Ac-susceptibility Measurements; DC Magnetic Susceptibility; Dianions; Electron Delocalization; Electron Transfer; Hyperfine Field; Larmor Precession; Low Temperatures; Macro-cyclic Ligands; Magnetic Exchange; Mixed Valence; Rapid Relaxation; Relaxation Frequency; Single Molecule; Single-molecule Magnet; Spectral Components; Spectral Properties; Temperature Dependence; Temperature Increase; Uniaxial Magnetic Anisotropy; Variable Temperature; Zero Fields; Algebra; Arrhenius Plots; Iron; Magnetic Anisotropy; Magnetic Susceptibility; Magnetism; Iron Compounds; Ferric Ion; Ferrous Ion; Chemical Structure; Chemistry; Electron; Magnetism; Mössbauer Spectroscopy; X Ray Crystallography; Crystallography; X-Ray; Electrons; Ferric Compounds; Ferrous Compounds; Magnetics; Models; Molecular; Spectroscopy; Mössbauer

International Standard Serial Number (ISSN)

0021-9606

Document Type

Article - Journal

Document Version

Final Version

File Type

text

Language(s)

English

Rights

© 2011 American Institute of Physics (AIP), All rights reserved.

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Chemistry Commons

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