Three new europium complexes, [Eu(PBI)3.3H2O] (1), [Eu(PBI)3.2TOPO] (2), and [Eu(PBI)3.2TPPO.H2O] (3) (where HPBI, TOPO, and TPPO stand for 3-phenyl-4-benzoyl-5-isoxazolone, tri-n-octylphosphine oxide, and triphenylphosphine oxide, respectively), with different neutral ligands were synthesized and characterized by elemental analysis, Fourier transform infrared, (1)H NMR, thermogravimetric analysis, and photoluminescence (PL) spectroscopy. The coordination geometries of the complexes were calculated using the Sparkle/AM1 (Sparkle Model for the Calculation of Lanthanide Complexes within the Austin Model 1) model. The ligand-Eu3+ energy-transfer rates were calculated in terms of a model of the intramolecular energy-transfer process in lanthanide coordination compounds reported in the literature. The room-temperature PL spectra of the europium(III) complexes are composed of the typical Eu3+ red emission, assigned to transitions between the first excited state (5D0) and the multiplet (7F(0-4)). On the basis of emission spectra and lifetimes of the 5D0-emitting level, the emission quantum efficiency (eta) was determined. The results clearly show that the substitution of water molecules by TOPO leads to greatly enhanced quantum efficiency (i.e., 26% vs 92%) and longer 5D0 lifetimes (250 vs 1160 micros). This can be ascribed to a more efficient ligand-to-metal energy transfer and a less nonradiative 5D0 relaxation process. Judd-Ofelt intensity parameters (Omega2 and Omega4) were determined from the emission spectra for the Eu3+ ion based on the 5D0 --> 7F2 and 5D0 --> 7F4 electronic transitions, respectively, and the 5D0 --> 7F1 magnetic-dipole-allowed transition was taken as the reference. A point to be noted in these results is the relatively high value of the Omega2 intensity parameter for all of the complexes. This may be interpreted as being a consequence of the hypersensitive behavior of the 5D0 --> 7F2 transition. The dynamic coupling mechanism is, therefore, dominant, indicating that the Eu3+ ion is in a highly polarizable chemical environment.

Visible-light sensitized luminescent europium(III) molecular materials are of considerable importance because their outstanding photophysical properties make them well suited as labels in fluorescence-based bioassays and low-voltage driven pure red-emitters in optoelectronic technology. One challenge in this field is development of visible-light sensitizing ligands that can form highly emissive europium(III) complexes with sufficient stability and aqueous solubility for practical applications. Indeed, some of the recent reports have demonstrated that the excitation-window can be shifted to longer-wavelengths in europium(III)-β-diketonate complexes by appropriate molecular engineering and suitably expanded π-conjugation in the complex molecules. In this review, attention is focused on the latest innovations in the syntheses and photophysical properties of visible-light sensitized europium(III)-β-diketonate complexes and their application as bioprobes for cellular imaging. Furthermore, luminescent nanomaterials derived from long-wavelength sensitized europium(III)-β-diketonate complexes and their application in life sciences are also highlighted.

3+ energy-transfer rates were calculated using a model of intramolecular energy transfer in lanthanide coordination complexes reported in the literature. The room-temperature PL spectra of the europium(III) complexes are com-