Remarkable chiral and luminescent properties of novel Yb(III) and Eu(III) complexes containing BINAPO ligand

Lanthanide complexes are of great importance for their prospective applications in wide range of science and technology. Chiral lanthanide complexes can constitute stereo-discriminating probes in biological media, owing to the luminescent properties of the rare-earth ions. Sensitized emission with narrow bandwidth, having fast radiation rate and high emission quantum efficiency are the main perspective for synthesizing the complexes. Attention has been given on remarkable chirality with high dissymmetry factors (g = Δεext/εmax) of the complexes. For this purpose, beta-diketonato ligands with chiral BINAPO (1,1′-binapthyl phosphine oxide) ligand were chosen to achieve the goal. The complexes [Ln(TFN)3(S-BINAPO)](TFN = 4,4,4-trifluoro-1(2-napthyl)-1,3-butanedione), [Ln(HFT)3(S-BINAPO)] (HFT = 4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)-1,3-hexanedione) and [Ln(HFA)3(S-BINAPO)](hfa = hexafluoroacetylacetonate) (where Ln = Yb, Eu) were synthesized. The complex, [Eu(TFN)3(S-BINAPO)] gives strong red emission at 615 nm with narrow emission band (<10 nm) when excited by 465 nm light with quantum efficiency 86%. The dissymmetry factors (g = Δεext/εmax) corresponding to the 7F1 → 5D0 transition at 590 nm is 0.091 for [Eu(TFN)3(S-BINAPO)] and for [Yb(hfa)3(S-BINAPO)](hfa = hexafluoroacetylacetonate) corresponding to the 2F7/2 → 2F5/2 transitions is 0.12, are among the largest values for both Eu and Yb complexes to date, respectively. The Eu complexes, [Eu(HFT)3(S-BINAPO)] and [Eu(TFN)3(S-BINAPO)] are found to be spontaneously emissive, showing bright red emission, when placed in sunlight or even in the laboratory when light is switched on.

Graphical abstractThe complexes [Ln(TFN)3(S-BINAPO)](TFN = 4,4,4-trifluoro-1(2-napthyl)-1,3-butanedione), [Ln(HFT)3(S-BINAPO)] (HFT = 4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)-1,3-hexanedione) and [Ln(hfa)3(S-BINAPO)](hfa = hexafluoroacetylacetonate) (where Ln = Yb, Eu), were synthesized, characterized and their remarkable chiral as well as luminescent properties are reported.Figure optionsDownload full-size imageDownload as PowerPoint slide