Issue 24, 2024

Engineered π⋯π interactions favour supramolecular dimers X@[FeL3]2 (X = Cl, Br, I): solid state and solution structure

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+.

Graphical abstract: Engineered π⋯π interactions favour supramolecular dimers X@[FeL3]2 (X = Cl, Br, I): solid state and solution structure

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Article information

Article type
Edge Article
Submitted
27 2 2024
Accepted
23 5 2024
First published
28 5 2024
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2024,15, 9047-9053

Engineered π⋯π interactions favour supramolecular dimers X@[FeL3]2 (X = Cl, Br, I): solid state and solution structure

A. Risa, L. A. Barrios, R. Diego, O. Roubeau, D. Y. Aleshin, Y. Nelyubina, V. Novikov, S. J. Teat, J. Ribas-Ariño and G. Aromí, Chem. Sci., 2024, 15, 9047 DOI: 10.1039/D4SC01365D

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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