Formation of Mono- and Polynuclear Luminescent Lanthanide Complexes based on the Coordination of Preorganized Phosphonated Pyridines

Abstract : A series of polynuclear assemblies based on ligand L (1,4,7-tris[hydrogen (6-methylpyridin-2-yl)phosphonate]-1,4,7-triazacyclononane) has been developed. The coordination properties of ligand L with LnIII (Ln = La, Eu, Tb, Yb, Lu) have been studied in water (pH = 7.0) and in D2O (pD = 7.0) by UV-absorption spectrometry, spectrofluorimetry, 1H and 31P NMR, DOSY, ESI-mass spectrometry, and X-ray diffraction. This nonadentate ligand forms highly stable mononuclear complexes in water and provides a very efficient shielding of the Ln cations, as emphasized by the very good luminescence properties of the Yb complex in D2O, especially regarding its lifetime (τD2O = 10.2 μs) and quantum yield (φD2O = 0.42%). In the presence of excess LnIII cation, polynuclar complexes of [(LnL)2Lnx] stoichiometry (x = 1 and x = 2) are observed in solution. In the solid state, a dinuclear complex of La could be isolated and structurally characterized by X-ray diffraction, unraveling the presence of strong hydrogen bonding interactions between a La(H2O)9 3+ cation and the [LaL]3- complex.
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Jérémy Salaam, Lilia Tabti, Sylvana Bahamyirou, Alexandre Lecointre, Oscar Hernandez Alba, et al.. Formation of Mono- and Polynuclear Luminescent Lanthanide Complexes based on the Coordination of Preorganized Phosphonated Pyridines. Inorganic Chemistry, American Chemical Society, 2018, 57 (10), pp.6095-6106. ⟨10.1021/acs.inorgchem.8b00666⟩. ⟨hal-01809157⟩

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