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http://hdl.handle.net/2445/208606
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DC Field | Value | Language |
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dc.contributor.author | Vidal, Daniel | - |
dc.contributor.author | Cirera Fernández, Jordi | - |
dc.contributor.author | Ribas Ariño, Jordi | - |
dc.date.accessioned | 2024-03-11T18:48:50Z | - |
dc.date.available | 2024-03-11T18:48:50Z | - |
dc.date.issued | 2023-03-20 | - |
dc.identifier.issn | 1463-9076 | - |
dc.identifier.uri | http://hdl.handle.net/2445/208606 | - |
dc.description.abstract | 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. | - |
dc.format.extent | 10 p. | - |
dc.format.mimetype | application/pdf | - |
dc.language.iso | eng | - |
dc.publisher | Royal Society of Chemistry | - |
dc.relation.isformatof | Reproducció del document publicat a: https://doi.org/10.1039/d3cp00250k | - |
dc.relation.ispartof | Physical Chemistry Chemical Physics, 2023, vol. 25, p. 12490-12499 | - |
dc.relation.uri | https://doi.org/10.1039/d3cp00250k | - |
dc.rights | cc-by-nc (c) Vidal, D. et al., 2023 | - |
dc.rights.uri | http://creativecommons.org/licenses/by-nc/3.0/es/ | * |
dc.source | Articles publicats en revistes (Ciència dels Materials i Química Física) | - |
dc.subject.classification | Òxid de ferro | - |
dc.subject.classification | Lligands | - |
dc.subject.classification | Propietats magnètiques | - |
dc.subject.other | Ferric oxide | - |
dc.subject.other | Ligands | - |
dc.subject.other | Magnetic properties | - |
dc.title | Fine-tuning of the spin-crossover properties of Fe(III) complexes via ligand design | - |
dc.type | info:eu-repo/semantics/article | - |
dc.type | info:eu-repo/semantics/publishedVersion | - |
dc.identifier.idgrec | 744053 | - |
dc.date.updated | 2024-03-11T18:48:50Z | - |
dc.rights.accessRights | info:eu-repo/semantics/openAccess | - |
Appears in Collections: | Articles publicats en revistes (Ciència dels Materials i Química Física) Articles publicats en revistes (Institut de Química Teòrica i Computacional (IQTCUB)) |
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846530.pdf | 638.92 kB | Adobe PDF | View/Open |
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