Synthesis and photoluminescence properties of heteroleptic Eu3+, Tb3+ and Tm3+ complexes

Five Eu(III), four Tb(III) and two Tm(III) multichromophoric complexes (1-Eu, 1-Tb, 2-Eu, 3-Eu, 3-Tb, 3-Tm, 4-Tb, 4-Tm, 5-Eu, 6-Eu and 6-Tb; where 1 = tris[dibenzoylmethanido] (4′-chloro-2,2′:6′,2′′-terpyridine), 2 = tris[dibenzoylmethanido] (4′-(9H-carbazol-9yl)-2,2′:6′,2′′-terpyridine), 3 = tris(1,1,1,5,5,5-hexafluoroacetylacetonato), 4 = tris[1,1,1,5,5,5-hexafluoroacetylacetonato] (tripyridin-2-ylamine), 5 = tris[dibenzoylmethanido][N-(4-(9H-carbazol-9-yl)butyl)-N-(dipyridin-2-yl)amine] and 6 = tris[dibenzoylmethanido][N-(6-(9H-carbazol-9-yl)hexyl)-N-(dipyridin-2-yl)amine]) emitting in the blue (Tm), green (Tb) and red (Eu) spectral regions, have been synthesized and characterized. The complexes involve five different coordinating (2,2′:6′,2′′-terpyridine (terpy); dibenzoylmethane (dbm); 1,1,1,5,5,5-hexafluoroacetylacetonato (hfa), tripyridin-2-ylamine (tri-amine) and N-(dipyridin-2-yl)amine (di-amine)) and one non-coordinating (carbazole) units. The synthesis and photophysical properties of these complexes are reported addressing the influence of the various ligands on the lanthanide metal-centered luminescence in CH2Cl2 solution and solid state matrices.