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Engineered π⋯π interactions favour supramolecular dimers X@[FeL 3 ] 2 (X = Cl, Br, I): solid state and solution structure.
- Source :
-
Chemical science [Chem Sci] 2024 May 28; Vol. 15 (24), pp. 9047-9053. Date of Electronic Publication: 2024 May 28 (Print Publication: 2024). - Publication Year :
- 2024
-
Abstract
- Ditopic bis-pyrazolylpyridine ligands usually react with divalent metal ions (M <superscript>2+</superscript> ) to produce dinuclear triple-stranded helicates [M <subscript>2</subscript> L <subscript>3</subscript> ] <superscript>4+</superscript> or, via π⋯π interactions, dimers of monoatomic complexes ([ML <subscript>3</subscript> ] <subscript>2</subscript> ) <superscript>4+</superscript> . 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 FeX <subscript>2</subscript> salts leads to crystallization of the tripartite high-spin assemblies (X@[Fe(L2) <subscript>3</subscript> ] <subscript>2</subscript> ) <superscript>3+</superscript> (X = Cl, Br or I). The aggregates exhibit exceptional stability, as confirmed by a combination of paramagnetic <superscript>1</superscript> H NMR techniques, demonstrating their persistence in solution. Our investigations further reveal that the guests Br <superscript>-</superscript> and I <superscript>-</superscript> are retained inside the associate in solution but Cl <superscript>-</superscript> is immediately released, resulting in the formation of the empty supramolecular dimer ([Fe(L2) <subscript>3</subscript> ] <subscript>2</subscript> ) <superscript>4+</superscript> .<br />Competing Interests: There are no conflicts to declare.<br /> (This journal is © The Royal Society of Chemistry.)
Details
- Language :
- English
- ISSN :
- 2041-6520
- Volume :
- 15
- Issue :
- 24
- Database :
- MEDLINE
- Journal :
- Chemical science
- Publication Type :
- Academic Journal
- Accession number :
- 38903210
- Full Text :
- https://doi.org/10.1039/d4sc01365d