A dinuclear europium(III) complex with thenoyltrifluoroacetonato and 1-(2-pyridylzao)-2-naphtholato ligands and its optical properties

Dinuclear lanthanide complexes of the general for Ln₂(TTA) ₄(PAN)₂ (Ln = Eu, Gd, Tb, Yb; TTA and monodeprotonated thenoyltrifluoroacetone and PAN 1-(2-pyridylazo)-2-naphthol, respectively) were prepared and structurally characterized. These novel complexes, representing the first examples of crystallographically characterized lanthanide-PAN complexes, each feature a dinuclear core with the metal atoms bridged by the phenolato O atoms of the chelating-bridging PAN ligands. Electronic spectroscopic and photoluminescence studies were carried out for the Eu(III) complex, and the results are consistent with ligand-mediated energy transfer and ligand-sensitized luminescence characteristic of Eu(III). The Eu(III) complex doped into a polymeric film was shown to effectively limit a nanosecond 523-nm laser pulse, and the limiting effect is rationalized in terms of reverse saturable absorption due to the strong absorption of the metal's excited triplet states that are populated by intersystem crossing.