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High-Field EPR Study of Resonance-Delocalized [Fe(2)(OH)(3)(tmtacn)(2)](2+)
Michael J. Knapp1, J. Krzystek, Louis-Claude Brunel
1Department of Chemistry and Biochemistry-0358, University of California at San Diego, La Jolla, California 92093, and the Center for Interdisciplinary Magnetic Resonance, National High Magnetic Field Laboratory, Tallahassee, Florida 32310.
Abstract:
High-frequency EPR data are reported for the Fe(II/III) valence delocalized dinuclear complex [Fe(2)(OH)(3)(tmtacn)(2)](2+). A full-matrix diagonalization approach is used to derive the spin-Hamiltonian parameters for this S(T) = (9)/(2) complex. At high fields (up to 14.5 T) and high frequencies (189-433 GHz) fine structure peaks due to resonances between the Kramers doublets (M(s) = (9)/(2), (7)/(2),.) are observed. The spacing of the fine structure reveals that the axial zero-field splitting (ZFS) parameter D is +1.08(1) cm(-)(1); a very small rhombic ZFS (|E|