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2023-03-20

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cc-by-nc (c) Vidal, D. et al., 2023
Si us plau utilitzeu sempre aquest identificador per citar o enllaçar aquest document: https://hdl.handle.net/2445/208606

Fine-tuning of the spin-crossover properties of Fe(III) complexes via ligand design

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Recurs relacionat

https://doi.org/10.1039/d3cp00250k

Resum

Exploring the chemical space of a given ligand aiming to modulate its ligand field strength is a versatile strategy for the fine-tuning of physical properties such as the transition temperature (T1/2) of spin- crossover (SCO) complexes. The computational study presented herein aims at systematically exploring the extent to which the ligand substituent effects can modulate T1/2 in two families of Fe(III) SCO systems with a N4O2 coordination environment and at identifying the best descriptors for fast and accurate prediction of changes in T1/2 upon ligand functionalization. B3LYP* calculations show that the attachment of substituents to b-ketoiminato fragments (L1) leads to drastic changes in T1/2, while functionalization of phenolato moieties (L2) allows for a finer degree of control over T1/2. Natural Bond Orbital (NBO) charges of the donor atoms, Hammett parameters for both para and meta- functionalization of L2, and Swain–Lupton parameters for L1 and para-functionalization of L2 have been found to be the suitable descriptors for predicting the changes in T1/2. Further analysis of the ligand-field splitting in such systems rationalizes the observed trends and shows that ligand substituents modify both the s and p bonds between the Fe(III) center and the ligands. Thus, we provide simple yet reliable guide- lines for the rational design of new SCO systems with specific values of T1/2 based on their ligand design.

Matèries

Òxid de ferro, Lligands, Propietats magnètiques

Matèries (anglès)

Ferric oxide, Ligands, Magnetic properties

Citació

Col·leccions

Articles publicats en revistes (Ciència dels Materials i Química Física)
Articles publicats en revistes (Institut de Química Teòrica i Computacional (IQTCUB))

Citació

VIDAL, Daniel, CIRERA FERNÁNDEZ, Jordi and RIBAS ARIÑO, Jordi. Fine-tuning of the spin-crossover properties of Fe(III) complexes via ligand design. Physical Chemistry Chemical Physics. 2023. Vol. 25, num. 12490-12499. ISSN 1463-9076. [consulted: 18 of August of 2026]. Available at: https://hdl.handle.net/2445/208606

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