.Single-Ion Magnetic Behaviour in an Iron(III) Porphyrin Complex: A Dichotomy Between High Spin and 5/2-3/2 Spin Admixture - Archive ouverte HAL Access content directly
Journal Articles Chemistry - A European Journal Year : 2020

.Single-Ion Magnetic Behaviour in an Iron(III) Porphyrin Complex: A Dichotomy Between High Spin and 5/2-3/2 Spin Admixture

Abstract

A mononuclear iron(III) porphyrin compound exhibiting unexpectedly slow magnetic relaxation, which is a characteristic of single-ion magnet behaviour, is reported. This behaviour originates from the close proximity (approximate to 550 cm(-1)) of the intermediate-spinS=3/2 excited states to the high-spinS=5/2 ground state. More quantitatively, although the ground state is mostlyS=5/2, a spin-admixture model evidences a sizable contribution (approximate to 15 %) ofS=3/2 to the ground state, which as a consequence experiences large and positive axial anisotropy (D=+19.2 cm(-1)). Frequency-domain EPR spectroscopy allowed them(S)= |+/- 1/2⟩->|+/- 3/2⟩ transitions to be directly accessed, and thus the very large zero-field splitting in this 3d(5)system to be unambiguously measured. Other experimental results including magnetisation, Mossbauer, and field-domain EPR studies are consistent with this model, which is also supported by theoretical calculations.
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Dates and versions

hal-02966985 , version 1 (21-11-2022)

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Marta Viciano-Chumillas, Geneviève Blondin, Martin Clémancey, Jurek Krzystek, Mykhaylo Ozerov, et al.. .Single-Ion Magnetic Behaviour in an Iron(III) Porphyrin Complex: A Dichotomy Between High Spin and 5/2-3/2 Spin Admixture. Chemistry - A European Journal, 2020, 26 (62), pp.14242-14251. ⟨10.1002/chem.202003052⟩. ⟨hal-02966985⟩
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