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- Title
Single‐Ion Magnetic Behaviour in an Iron(III) Porphyrin Complex: A Dichotomy Between High Spin and 5/2–3/2 Spin Admixture.
- Authors
Viciano‐Chumillas, Marta; Blondin, Geneviève; Clémancey, Martin; Krzystek, Jurek; Ozerov, Mykhaylo; Armentano, Donatella; Schnegg, Alexander; Lohmiller, Thomas; Telser, Joshua; Lloret, Francesc; Cano, Joan
- 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 (≈550 cm−1) of the intermediate‐spin S=3/2 excited states to the high‐spin S=5/2 ground state. More quantitatively, although the ground state is mostly S=5/2, a spin‐admixture model evidences a sizable contribution (≈15 %) of S=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 the mS= |±1/2⟩→|±3/2⟩ transitions to be directly accessed, and thus the very large zero‐field splitting in this 3d5 system to be unambiguously measured. Other experimental results including magnetisation, Mössbauer, and field‐domain EPR studies are consistent with this model, which is also supported by theoretical calculations.
- Subjects
PORPHYRINS; IRON; MAGNETIC relaxation; ELECTRON paramagnetic resonance spectroscopy; BEHAVIOR; METALLOPORPHYRINS
- Publication
Chemistry - A European Journal, 2020, Vol 26, Issue 62, p14242
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.202003052