Engineered π⋯π interactions favour supramolecular dimers $\mathrm{X@[FeL_{3}]_{2}(X = Cl, Br, I)}$: solid state and solution structure
Ditopic bis-pyrazolylpyridine ligands usually react with divalent metal ions ($\mathrm{M^{2+}}$) to produce dinuclear triple- stranded helicates $\mathrm{[M_{2}L_{3}]^{4+}}$ or, via $\mathrm{\pi\cdots\pi}$ interactions, dimers of monoatomic complexes $\mathrm{([ML_{3}]_{2})^{4+}}$. The introduction...
| Autores: | , , , , , , , , , |
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| Tipo de recurso: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2024 |
| País: | España |
| Institución: | Universidad de Oviedo (UNIOVI) |
| Repositorio: | Dipòsit Digital de la UB |
| OAI Identifier: | oai:dnet:ubarcelona__::bdd1687ea6949cc9a5a1beb445862cb1 |
| Acceso en línea: | https://hdl.handle.net/2445/229266 |
| Access Level: | acceso abierto |
| Palabra clave: | Interaccions hiperfines Cristalls moleculars Química supramolecular Hyperfine interactions Molecular crystals Supramolecular chemistry |
| Sumario: | Ditopic bis-pyrazolylpyridine ligands usually react with divalent metal ions ($\mathrm{M^{2+}}$) to produce dinuclear triple- stranded helicates $\mathrm{[M_{2}L_{3}]^{4+}}$ or, via $\mathrm{\pi\cdots\pi}$ interactions, dimers of monoatomic complexes $\mathrm{([ML_{3}]_{2})^{4+}}$. The introduction of an additional benzene ring at each end of ligand L increases the number of aromatic contacts within the supramolecular aggregate by 40%, driving the self-recognition process in an irreversible manner. Consequently, the mixing of new bis-pyrazolylquinoline L2 with $\mathrm{FeX_{2}}$ salts leads to crystallization of the tripartite high-spin assemblies $\mathrm{(X@[Fe(L2)_{3}]_{2})^{3+}(X = Cl, Br or I)}$. The aggregates exhibit exceptional stability, as confirmed by a combination of paramagnetic $\mathrm{^{1}H}$ NMR techniques, demonstrating their persistence in solution. Our investigations further reveal that the guests$\mathrm{Br^{-}}$ and $\mathrm{I^{-}}$ are retained inside the associate in solution but $\mathrm{Cl^{-}}$ is immediately released, resulting in the formation of the empty supramolecular dimer $\mathrm{([Fe(L2)_{3}]_{2})^{4+}}$ |
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