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Updated: Jun 23, 2025
From Molecules to Materials: Engineering New Ionic Liquid Crystals Through Halogen Bonding
Published on: March 24, 2018
Engineered π⋯π interactions favour supramolecular dimers X@[FeL3]2 (X = Cl, Br, I): solid state and solution
Arnau Risa1, Leoní A Barrios1,2, Rosa Diego1,2
1Departament de Química Inorgànica i Orgànica, Secció Química Inorgànica, Universitat de Barcelona Barcelona Spain leoni.barrios@ub.edu novikov@ub.edu aromi@ub.edu.
Abstract:
Ditopic bis-pyrazolylpyridine ligands usually react with divalent metal ions (M2+) to produce dinuclear triple-stranded helicates [M2L3]4+ or, via π⋯π interactions, dimers of monoatomic complexes ([ML3]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 FeX2 salts leads to crystallization of the tripartite high-spin assemblies (X@[Fe(L2)3]2)3+ (X = Cl, Br or I). The aggregates exhibit exceptional stability, as confirmed by a combination of paramagnetic 1H NMR techniques, demonstrating their persistence in solution. Our investigations further reveal that the guests Br- and I- are retained inside the associate in solution but Cl- is immediately released, resulting in the formation of the empty supramolecular dimer ([Fe(L2)3]2)4+.
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