Tuning Selectivity and Stability in Heteroleptic Lanthanide Adducts by Ligand Design.

Terdentate ligands L10-L14 and their heteroleptic [LkLn(hfac)3] complexes (Ln = La, Eu, Gd, Er, or 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 in which larger thermodynamic formation constants with lanthanides in CD2Cl2 are accompanied by an unexpected decrease in 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 position 1 of the benzimidazole moieties in L13 and L14, which is accompanied by an optimization of metal-nitrogen bond lengths. This study contributes to the rational design of highly stable neutral heteroleptic lanthanide ß-diketonate adducts that resist dissociation in solution, a prerequisite for photophysical applications using these highly luminescent systems at the molecular level.

Symmetry and Rigidity for Boosting Erbium-Based Molecular Light-Upconversion in Solution.

Previously limited to highly symmetrical homoleptic triple-helical complexes [Er(Lk)3 ]3+ , where Lk are polyaromatic tridentate ligands, single-center molecular-based upconversion using linear optics and exploiting the excited-state absorption mechanism (ESA) greatly benefits from the design of stable and low-symmetrical [LkEr(hfa)3 ] heteroleptic adducts (hfa- =hexafluoroacetylacetonate anion). Depending on (i) the extended π-electron delocalization, (ii) the flexibility and (iii) the heavy atom effect brought by the bound ligand Lk, the near-infrared (801 nm) to visible green (542 nm) upconversion quantum yield measured for [LkEr(hfa)3 ] in solution at room temperature can be boosted by up to three orders of magnitude.