Chemical and physical behaviour of heteroleptic 2,6-bis(1 H -benzimidazol-2-yl)pyridine and 2,2′:6′,2″-terpyridine substituted tricyclophosphazene ruthenium(II) complexes

Davidson, Ross J.; Ainscough, Eric W.; Brodie, Andrew M.; Jameson, Geoffrey B.; Waterland, Mark R.

doi:10.1016/j.poly.2015.02.018

Cited by 3 publications

(1 citation statement)

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“…A similar but monodeprotonated [Cp*Rh( L10 -H)Cl] side product (Tables S5–S8, Figure b, and Figure S108) is observed after purification by chromatography on Al 2 O 3 when [Cp*RhCl 2 ] 2 is used as the catalyst. In agreement with previous studies, − L10 becomes sufficiently acidic upon complexation to Rh(III) to be deprotonated by Al 2 O 3 during the purification procedure. In summary, the failure of the rhodium-catalyzed reaction is systematically observed when using 1,2-dichloroethane (DCE), MeOH, and DMSO as nonpolar, polar protic, and polar aprotic solvents, respectively.…”

Section: Resultsmentioning

confidence: 99%

Tuning Selectivity and Stability in Heteroleptic Lanthanide Adducts by Ligand Design

Le-Hoang,

Guénée,

Sommer

et al. 2024

Inorg. Chem.

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Terdentate ligands L10–L14 and their heteroleptic [L k Ln(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 β-diketonate adducts that resist dissociation in solution, a prerequisite for photophysical applications using these highly luminescent systems at the molecular level.

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Section: Resultsmentioning

confidence: 99%