Single-Ion Magnetic Behaviour in an Iron(III) Porphyrin Complex: A Dichotomy Between High Spin and 5/2-3/2 Spin Admixture.
Chemistry
; 26(62): 14242-14251, 2020 Nov 06.
Article
en En
| MEDLINE
| ID: mdl-32649799
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 (≈550â
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=+19.2â
cm-1 ). Frequency-domain EPR spectroscopy allowed the mS = |±1/2⟩â|±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.
Texto completo:
1
Colección:
01-internacional
Banco de datos:
MEDLINE
Tipo de estudio:
Prognostic_studies
Idioma:
En
Revista:
Chemistry
Asunto de la revista:
QUIMICA
Año:
2020
Tipo del documento:
Article
País de afiliación:
España