Scientific article

Tuning Selectivity and Stability in Heteroleptic Lanthanide Adducts by Ligand Design

Published inInorganic chemistry, vol. 63, no. 8, p. 3712-3723
Publication date2024-02-09
First online date2024-02-09

The terdentate ligands L10-L14 and their heteroleptic [LkLn(hfac) 3 ] complexes (Ln = La, Eu, Gd, Er, Y; H-hfac = 1,1,1,5,5,5-hexafluoropentane-2,4-dione) exhibit multifactorial correlations between the ligand’s structural frameworks, including their level of preorganization and steric congestion, and their affinities and selectivities for catching the trivalent lanthanide containers [Ln(hfac) 3 ]. The polyaromatic ligand scaffolds could be stepwise modulated via lanthanide-template synthetic strategies using intermolecular rhodium-catalyzed insertion reactions. The increasing level of preorganization along the L10→L11→L12 series leads to a duality where larger thermodynamic formation constants with lanthanides in CD2 Cl2 are accompanied by an unexpected decrease of the Ln-N affinities in the solid state, which could be assigned to a limited match between the lanthanide size and the enlarged preorganized cavities. On the contrary, a reduced stability is induced by the connection of additional methyl groups at the 1-position of the benzimidazole moieties in L13 and L1, which is accompanied by an optimization of metal-nitrogen bond lengths. This study contributes to the rational design of highly stable neutral heteroleptic lanthanide -diketonate adducts which resist dissociation in solution; a prerequisite for photophysical applications using these highly luminescent systems at the molecular level.

Citation (ISO format)
LE, Hoang Giau et al. Tuning Selectivity and Stability in Heteroleptic Lanthanide Adducts by Ligand Design. In: Inorganic chemistry, 2024, vol. 63, n° 8, p. 3712–3723. doi: 10.1021/acs.inorgchem.3c03710
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Article (Accepted version)
accessLevelRestrictedaccessLevelPublic 02/10/2025
ISSN of the journal0020-1669

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