Lanthanide hexafluoroacetylacetonates vs. nitrates for the controlled loading of luminescent polynuclear single-stranded oligomers

Abstract : This work demonstrates how minor structural and electronic changes between Ln(NO3)3 and Ln(hfac)3 lanthanide carriers (Ln = trivalent lanthanide, hfac = hexafluoroacetylacetonate) lead to opposite thermodynamic protocols for the metal loading of luminescent polynuclear single-stranded oligomers. Whereas metal clustering is relevant for Ln(hfac)3, the successive fixation of Ln(NO3)3 provides stable microspecies with an alternated occupancy of the binding sites. Partial anion dissociation and anion/ligand bi-exchange processes occur in polar aprotic solvents, which contribute to delay the unambiguous choice of a well-behaved neutral lanthanide carrier for the selective complexation of different trivalent lanthanides along a single ligand strand. Clues for further improvement along this stepwise strategy are discussed.
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Submitted on : Wednesday, April 24, 2013 - 5:11:30 PM
Last modification on : Wednesday, April 17, 2019 - 3:00:05 PM

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A. Zaim, N.D Favera, L. Guenee, H. Nozary, T.N.Y. Hoang, et al.. Lanthanide hexafluoroacetylacetonates vs. nitrates for the controlled loading of luminescent polynuclear single-stranded oligomers. Chemical Science , The Royal Society of Chemistry, 2013, 4 (3), pp.1125-1136. ⟨10.1039/C2SC21982D⟩. ⟨hal-00817505⟩

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