CSIRO Publishing, Australian Journal of Chemistry, 10(62), p. 1300, 2009
DOI: 10.1071/ch09314
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The luminescence properties of lanthanoid ions can be dramatically enhanced by coupling them to antenna ligands that absorb light in the UV-visible and then efficiently transfer the energy to the lanthanoid centre. The synthesis and the complexation of Ln{sup III} cations (Ln = Eu, Gd) for a ligand based on four 1-hydroxy-2-pyridinone (1,2-HOPO) chelators appended to a ligand backbone derived by linking two L-lysine units (3LI-bis-LYS) is described. This octadentate Eu{sup III} complex ([Eu(3LI-bis-LYS-1,2-HOPO)]{sup -}) has been evaluated in terms of its thermodynamic stability, UV-visible absorption and luminescence properties. For this complex, the conditional stability constant (pM) is 19.9, which is an order of magnitude higher than diethylenetriaminepentacetic acid at pH = 7.4. This Eu{sup III} complex also shows an almost two-fold increase in its luminescence quantum yield in aqueous solution (pH = 7.4) when compared with other octadentate ligands. Hence, despite a slight decrease of the molar absorption coefficient, a much higher brightness is obtained for [Eu(3LI-bis-LYS-1,2-HOPO)]{sup -}. This overall improvement was achieved by saturating the coordination sphere of the Eu{sup III} cation, yielding an increased metal-centred efficiency by excluding solvent water molecules from the metal's inner sphere.