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Engineered π⋯π interactions favour supramolecular dimers $\mathrm{X@[FeL_{3}]_{2}(X = Cl, Br, I)}$: solid state and solution structure
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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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RISA, Arnau, et al. Engineered π⋯π interactions favour supramolecular dimers $\mathrm{X@[FeL_{3}]_{2}(X = Cl, Br, I)}$: solid state and solution structure. Chemical Science. 2024. Vol. 15, num. 24, pags. 9047-9053. ISSN 2041-6520. [consulted: 22 of May of 2026]. Available at: https://hdl.handle.net/2445/229266