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Single-Crystal High-Frequency Electron Paramagnetic Resonance Investigation of a Tetranuclear Iron(III) Single-Molecule Magnet

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Department of Physics, University of Antwerp (UIA), Universiteitsplein 1, 2610 Antwerp, Belgium, Department of Chemistry, University of Florence, Via Maragliano 77, 50144 Florence, Italy, and Institute of Atomic Physics (NIMP), POB MG-7 Magurele, 76900 Bucharest, Romania
Cite this: J. Phys. Chem. B 2001, 105, 13, 2658–2663
Publication Date (Web):March 14, 2001
Copyright © 2001 American Chemical Society

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    A high-frequency (95 GHz) electron paramagnetic resonance (EPR) study is reported on single crystals of the planar tetranuclear complex Fe4(OCH3)6(dpm)6 (where Hdpm = dipivaloylmethane), which has been previously shown to present typical single-molecule magnet behavior. The spectra, all originating from the S = 5 ground state, possess quasi-axial symmetry along the normal to the plane defined by the four Fe(III) ions. The measured spectra are shown to belong to three different structural variations of the compound, resulting from disorder in the ligands around two of the Fe(III) ions. Accurate values could be obtained for the second- and fourth-order crystal field parameters related to the parallel EPR spectra, while the other parameters could be determined only for the dominant species. The separation between individual lines is decreasing and vanishing with increasing temperature. This effect is attributed to the contribution of fast relaxing excited states, whose population is varying with temperature.

     University of Antwerp.

     University of Florence.


    In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.


     Institute of Atomic Physics.

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