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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...
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