Eu(III) Complexes of Octadentate 1-Hydroxy-2-pyridinones: Stability and Improved Photophysical Performance[].
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 center. The synthesis and the complexation of Ln(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(III) complex ([Eu(3LI-bis-LYS-1,2-HOPO)](-)) 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 (DTPA) at pH= 7.4. This Eu(III) complex also shows an almost two-fold increase in its luminescence quantum yield in aqueous solution (pH= 7.4) when compared to 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)](-). This overall improvement was achieved by saturating the coordination sphere of the Eu(III) cation, yielding an increased metal centered efficiency by excluding solvent water molecules from the metal's inner sphere.
Moore
Evan G
EG
Chemical Sciences Division, Lawrence Berkeley National Laboratories, 1 Cyclotron Road, Mail Stop 70A1150, Berkeley, CA, 94720.
D'Aléo
Anthony
A
Xu
Jide
J
Raymond
Kenneth N
KN