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Zaim A., Natalia Dalla F., Guenee L., Nozary H., Hoang Thi Nhu Y., Svetlana V. E., Petoud S. and Piguet C.

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

Chemical Science 4 (3) 1125-1136

par Frapart - publié le , mis à jour le

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.