Surprisingly bright near-infrared luminescence and short radiative lifetimes of ytterbium in hetero-binuclear Yb-Na chelates.
New heterobinuclear lanthanide complexes with benzoxazole-substituted 8-hydroxyquinolines, [Ln(ligand)(2)(mu-ligand)(2)Na] (Ln: Yb, Lu), have been prepared and their structure established by X-ray crystallography, (1)H NMR spectroscopy, and photophysical studies. The complexes display efficient ligand-sensitized near-infrared luminescence of ytterbium at 925-1075 nm with lifetimes and quantum yields as high as 22 micros and 3.7%, in the solid state, and 20 micros and 2.6% in CH(2)Cl(2) solution, respectively. These quantum yields are the highest reported to date for ytterbium complexes with organic ligands containing C-H bonds. A long-wavelength and intense intraligand charge-transfer transition (lambda(max) = 446-456 nm; epsilon approximately 1.2 x 10(4) M(-1) cm(-1)) allows for the excitation of infrared luminescence with visible light up to 600 nm. Remarkable features of these complexes include (i) quantitative ligand-to-Yb(III) energy transfer resulting in high overall efficiency of the ytterbium luminescence, (ii) unusually short radiative lifetime of the Yb(III) ion, 706-745 micros for solutions in CH(2)Cl(2), calculated from the f-f absorption spectra, and 513-635 micros estimated for solid state samples from quantum yield and lifetime data, and (iii) the unexpected large influence of second-sphere composition on the radiative lifetime of ytterbium.
Shavaleev
Nail M
NM
Ecole Polytechnique Fédérale de Lausanne, Laboratory of Lanthanide Supramolecular Chemistry, BCH 1405, CH-1015 Lausanne, Switzerland.
Scopelliti
Rosario
R
Gumy
Frédéric
F
Bünzli
Jean-Claude G
JC