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Scientific article
English

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
Abstract

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.

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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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accessLevelRestrictedaccessLevelPublic 02/10/2025
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ISSN of the journal0020-1669
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